Monitoraggio e analisi dei metalli pesanti nei fiumi Rokytkae Botica Praga (Repubblica Ceca)

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Monitoring and analysis of heavy metals in Rokytka and Botic creeks in Prague (Czech Republic)

Monitoraggio e analisi dei metalli pesanti nei fiumi Rokytka e Botic a Praga (Repubblica Ceca)

Università degli Studi di Napoli

Federico II

Relatore Prof. Massimiliano Fabbricino

Prof. Jana Nabelkova Correlatore

Ing. Marco Race

Candidati

Iavarone Vincenzo M67/429 Mentoglio Giorgia M67/411

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Monitoraggio delle acque

• Nutrienti^:

Azoto e Fosforo

• Metalli pesanti^:

Hg, Zn, Cu, Pb, Cd, Cr, Ni

Sostanze inquinanti

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Descrizione area di studio

Campionamento

Analisi di laboratorio (AAS)

Quadro Normativo

Parametri chimici

Metalli Pesanti

 Analisi di laboratorio (Hg)

 Metalli Pesanti (Hg)

 Sostanza organica

 Confronto con dati storici

 Principali fonti di inquinamento

 Conclusioni

Organizzazione presentazione

1°fase 2°fase

(4)

Area di studio

Rokytka

Sampling site Locality description

RP1 spring close to vilage Tehovec

RP2 below the Tehovec village, surface runoff from road RP3 below pond Jureček, Radošovice village

RP4 below Říčany village RP5 below Běchovice village RP6 above Kyjsky pond (Prague)

RP7 below Kyjsky pond

RP8 above a Combined sewer overfow (OK 33E Pod Taborem) R9 below a Combined sewer overfow (OK 33E Pod Taborem) R10 below revitalised section of Rokytka

R11 before entering Vltava

1° campionamento: 28 Marzo 2018 2° campionamento: 24 Maggio 2018

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Area di studio

Botic

Sampling

site Locality description

BP 1 spring

BP 2 below 1st pond

BP 3 above village Cenetice, surrounded by farm fields BP 4 below 1st tributary and village Cenetice

BP 5 above 2nd tributary BP 6 below 2nd tributary

BP 7 close to Prague highway ring, cottage area in surrounding BP 8 below 3rd tributary

BP 9 below 4th tributary

BP 10 above the Pruhonice garden

BP 11 below retention pond for highway runoff BP 12 above 5th tributary

BP 13 below 5th tributary

BP 14 below retention pond of SWD - runoff from housing estate area BP 15 below CSO 1, app. 1 km below the Hostivar reservoir

BP 16 below SWDs above CSO 2 BP 17 below CSO 2

BP 18 car repair shop

BP 19 below SWDs from heavy traffic area, below the Hamersky pond BP 20 above pipeline

1° campionamento: 13 Aprile 2018 2° campionamento: 25 Maggio 2018

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Campionamento

In sito:

•pH

•Conduttività

•Temperatura

•Ossigeno disciolto

In laboratorio:

• Durezza e alcalinità

• COD, Cl^-, NH⁴⁺-N, NO^3- - N, PO₄^3- -P

• Metalli pesanti

• Mercurio

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1.Congelamento a -20°C

Trattamento sedimenti

2. Liofilizzazione

3. Setacciamento

4. Digestione

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Spettroscopia ad assorbimento atomico

• Valore medio;

• Deviazione standard relativa (RSD).

• Ni • Pb • Cu • Zn • Cd • Cr

(9)

oC_s= Concentrazione metallo nei sedimenti [mg/Kg]

oC_w=Concentrazione metallo in acqua [mg/L]

Elaborazione dati

Coefficiente di distribuzione K_d

K_d= ^𝐶^𝑠

𝐶_𝑤 ^o^{Log K}^d < 3 – Forma disciolta

o3 < Log K_d < 4 – Forma sospesa

oLog K_d > 4 – Legato alla frazione solida

Coefficiente di Pearson ρ

𝜌_𝑋𝑌 = 𝑐𝑜𝑣(𝑋, 𝑌 𝜎_𝑋𝜎_𝑌

oCov(X,Y)= Covarianza tra X e Y o σ_x e σ_y = Deviazioni standard

o Se 𝜌_𝑋𝑌 < 0.3 debole

o Se 0.3 < 𝜌_𝑋𝑌 < 0.7 moderata o Se 𝜌_𝑋𝑌 > 0.7 forte

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Quadro normativo

Limite EQS

Cd 0,592 mg/Kg TEC 11,7 mg/Kg PEC

Cr 56 mg/Kg TEC

159 mg/Kg PEC

Cu 28 mg/Kg TEC

77,7 mg/Kg PEC Ni 39,6 mg/Kg TEC 38,5 mg/Kg PEC Pb 34,2 mg/Kg TEC 396 mg/Kg PEC Hg 0,18 mg/Kg TEC 1,06 mg/Kg PEC

Zn 159 mg/Kg TEC

1539 mg/Kg PEC

Limite

Temperatura < 29 °C

pH 5-9 ^-

Conduttività 110 mS/m

OD > 9 mg/l

COD 26 mg/l

PO₄^3--P 0,15 mg/l

NO^3-- N 5,4 mg/l

NH⁴⁺-N 0,23 mg/l

Cl^- 150 mg/l

Mg 120 mg/l

Ca 190 mg/l

Cd 0,45 µg/l

Cr 18 µg/l

Cu 14 µg/l

Ni < 34 µg/l

Pb < 14 µg/l

Hg < 0,07 µg/l

Zn 92 µg/l

Sedimenti

Acqua

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Parametri Chimici Fosfati e Nitrati

village village,runoff pond village village Kyjsky pond CSO revitalized entering Vltava

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

1 2 3 4 5 6 7 8 9 10 11

P-Po3 4-[mg/l]

Sampling site

Rokytka

28.3.18 24.5.18 Cz.Gov.401/2015

village village,runoff pond village village Kyjsky pond CSO revitalised entering Vltava

0,0 2,0 4,0 6,0 8,0 10,0 12,0 14,0 16,0

1 2 3 4 5 6 7 8 9 10 11

N-No 3-[mg/l]

Sampling site

spring 1st pond village Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice garedn highway runoff 5th tributary SWD Hostivar r. CSO car repair shop SWDSWD pipeline

0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 N-NO 3-[mg/l]

Sampling site

spring 1st pond village Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice garden highway runoff 5th tibutary SWD Hostivar reservoir SWD CSO car repair shop SWD pipeline

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 P-PO 43-[mg/l]

Sampling site

Botic

13.4.18 23.5.18 Cz.Gov.401/2015

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Parametri Chimici

Ossigeno disciolto e COD

spring 1st pond v. Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice g. highway runoff 5th tributary SWD CSO car repair shop SWD

SWD Hostivar res. pipeline

0,0 2,0 4,0 6,0 8,0 10,0 12,0 14,0 16,0

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

DO [mg/l]

Sampling site

Botic

13.4.18 23.5.18 Cz.Gov.401/2015

0 10 20 30 40 50 60

1 2 3 4 5 6 7 8 9 10 11

COD [mg/l]

Sampling site

spring 1 st pond village Cenetice 1 st trubutary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice garden highway runoff 5th tributary SWD CSO car repair shop

Hostivar reservoir SWD pipeline

0,0 10,0 20,0 30,0 40,0 50,0 60,0

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

COD [mg/l]

Sampling site

village village,runoff pond village village Kyjsky pond

0 5 10 15 20 25

1 2 3 4 5 6 7 8 9 10 11

DO [mg/l]

Sampling site

Rokytka

28.3.18 24.5.18 Cz.Gov.401/2015

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0 5 10 15 20 25 30 35 40 45

1 2 3 4 5 6 7 8 9 10 11

Ni [mg/Kg]

Sampling site

Rokytka

28.3.18 24.5.18 TEC

Metalli pesanti nei sedimenti Nichel e Piombo

0 50 100 150 200 250 300 350 400

1 2 3 4 5 6 7 8 9 10 11

Pb [mg/Kg]

Sampling site

spring 1st pond village Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice garden highway runoff 5th tributary SWD Hostivar reservoir SWD CSO car repair shop SWD pipeline

0 5 10 15 20 25 30 35 40 45

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Ni [mg/Kg]

Sampling site

Botic

13.4.18 23.5.18 TEC

0 50 100 150 200 250 300

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Pb [mg/Kg]

Sampling site

K_d=3,6

K_d=3,5

K_d= 4,5

K_d=4,3

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0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7

1 2 3 4 5 6 7 8 9 10 11

Cd [mg/Kg]

Sampling site

Rokytka

28.3.18 24.5.18 TEC

0 50 100 150 200 250

1 2 3 4 5 6 7 8 9 10 11

Cr [mg/Kg]

Sampling site

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Cd [mg/Kg]

Sampling site

Botic

13.4.18 23.5.18 TEC

0 10 20 30 40 50 60

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Cr [mg/Kg]

Sampling site

Metalli pesanti nei sedimenti Cadmio e Cromo

K_d=4-4,5

K_d=3,4

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0 100 200 300 400 500

1 2 3 4 5 6 7 8 9 10 11

Cu [mg/Kg]

Sampling site

Rokytka

28.3.18 24.5.18 TEC PEC

0 50 100 150 200 250

1 2 3 4 5 6 7 8 9 10 11

Zn [mg/Kg]

Sampling site

0 50 100 150 200 250 300 350

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Cu [mg/Kg]

Sampling site

Botic

13.4.18 23.5.18 TEC PEC

spring 1st pond village Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice garden highway runoff 5th tributary SWD Hostivar reservoir SWD CSOcar repair shop SWD pipeline

0 100 200 300 400 500 600 700 800

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Zn [mg/Kg]

Sampling site

Metalli pesanti nei sedimenti Rame e Zinco

K_d= 4,0 K_d= 3,5

K_d= 4,6

K_d= 4,5

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Organizzazione presentazione

 Analisi di laboratorio (Hg)

 Metalli Pesanti (Hg)

 Sostanza organica

 Confronto con dati storici

 Principali fonti di inquinamento

 Conclusioni

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Advanced mercury analyzer AMA 254

• Campioni di sedimenti:

100 mg-200 mg

• Campioni di acqua: 100 µl

(18)

Metalli pesanti Mercurio

0,0 0,1 0,2 0,3 0,4 0,5 0,6

1 2 3 4 5 6 7 8 9 10 11

Hg [mg/Kg]

Sampling site

Rokytka

28.3.18 24.5.18 TEC

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

1 2 3 4 5 6 7 8 9 10

Hg

Sampling site

0,206-0,600 mm 0,063-0,206 mm

< 0,063 mm

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Hg [mg/Kg]

Sampling site

Botic

13.4.18 23.5.18 TEC

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Hg

Sampling site 0,206-0,600 mm

0,063-0,206 mm

< 0,063 mm

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Metalli pesanti Mercurio

0,0000 0,0010 0,0020 0,0030 0,0040 0,0050 0,0060 0,0070 0,0080 0,0090 0,0100

1 2 3 4 5 6 7 8 9 10 11

Hg [mg/l]

Sampling site

Rokytka

28.3.18 24.5.18 Cz.Gov.401/2015

spring 1st pond vi. Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice garden highway runoff 5th tributary SWD Hostivar r. SWD CSO car repair shop SWD pipeline

0,00000 0,00005 0,00010 0,00015 0,00020 0,00025 0,00030

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Hg [mg/l]

Sampling site

Botic

13.4.18 23.5.18 Cz.Gov.401/2015

overall R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 R11

1°

2°

1,4 0,9

2,4 2,4

2,2 2,5

2,1 2,4

2,5 2,6

2,5 -0,02

2,6 3,0

2,9 2,9

3,3 3,0

3,1 3,4

2,6

overall BP1 BP2 BP3 BP4 BP5 BP6 BP7 BP8 BP9 BP10

1°

2°

2,4 2,4

2,6 2,5

2,4 0,03

2,3 2,6

2,6 2,6

2,5 3,7

2,5 2,2

2,6 2,3

2,5 2,4

overall BP11 BP12 BP13 BP14 BP15 BP16 BP17 BP18 BP19 BP20

1°

2°

2,8 2,8

2,8 2,4

2,6 2,8

2,2 2,7

2,4 3,3

2,6 2,6

4,1 3,2

3,3 3,5

2,7 3,0

3,0 3,4

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Sostanza organica LOI

1. Preparazione campioni;

2. Riscaldamento a 550°C per 4 ore;

3. Raffreddamento in essiccatore;

4. Calcolo LOI.

LOI (%)= ^∆𝑚

𝑚𝑠 ∗ 100

- ms=m2-m0

- Δm : peso perso dopo riscaldamento a 550°C (g) - m0 : peso vaso di terracotta (g)

- m1 : peso campione + peso vaso (g)

- m2 : peso campione + peso vado dopo riscadamento a 550°C (g) - mS : peso di campione asciutto (g)

(21)

0%

5%

10%

15%

20%

25%

1 2 3 4 5 6 7 8 9 10 11

OM %

Sampling site

Rokytka

28.3.18

24.5.18

Sostanza organica

village Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice garden highway runoff 5th tributary SWD Hostivar reservoir SWD CSO car repair shop SWD pipeline

0%

5%

10%

15%

20%

25%

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

OM%

Sampling site

Botic

13.4.18

25.5.18

spring 1st pond

village village,runoff pond village village Kyjsky pond CSO revitalized

0 0,05 0,1 0,15 0,2 0,25

0 5 10 15 20 25 30

1 2 3 4 5 6 7 8 9 10

OM [mg/Kg]

Ni [mg/Kg]

Sampling site ^Ni

OM

spring 1st pond village Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice g. highway runoff 5th tributary SWD Hotivar reservoir SWD CSO car repair shop SWD pipeline

0 5 10 15 20 25

0,0 0,1 0,1 0,2 0,2 0,3

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Ni [mg/Kg]

OM [mg/Kg]

Sampling site OM Ni

Ρ²= 0,8 Ρ¹= 0,6

(22)

Confronto con dati storici Botic

Riserva Hostivar

0 10 20 30 40

Conc. [µg/l]

Pb

0 50 100 150 200 250 300 350

Conc. [mg/Kg]

Pb

0 20 40 60

Conc. [µg/l]

Cu

0 200 400 600 800

Conc [mg/Kg]

Zn

0 0,05 0,1 0,15 0,2 0,25

Conc. [mg/l]

Hg

0 0,2 0,4 0,6 0,8 1

Conc. [mg/lKg]

Hg

Sito 18

(23)

0 20 40 60 80 100 120 140 160

0 50 100 150 200 250

1 2 3 4 5 6 7 8 9 10

Cu [mg/Kg]

Zn [mg/Kg]

Sampling site

Rokytka

Zn Cu

spring 1st pond village Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice garden highway runoff 5th tributary SWD Hotivar reservoir SWD CSO car repair shop SWD pipeline

0 20 40 60 80 100 120 140 160 180

0 100 200 300 400 500 600 700 800

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Cu [mg/Kg]

Zn [mg/Kg]

Sampling site

Botic

Zn Cu

Principali fonti di inquinamento Rokytka e Botic

Cd Cu Ni Pb Hg Cr Zn

Cd 1,00 0,91 0,22 0,13 0,21 0,25 0,89

Cu 0,91 1,00 0,21 0,13 0,24 0,15 0,97

Ni 0,22 0,21 1,00 -0,16 -0,14 0,42 0,28

Pb 0,13 0,13 -0,16 1,00 -0,07 -0,06 0,13

Hg 0,21 0,24 -0,14 -0,07 1,00 0,06 0,17

Cr 0,25 0,15 0,42 -0,06 0,06 1,00 0,11

Zn 0,89 0,97 0,28 0,13 0,17 0,11 1,00

ρ_Cu,Zn=0.97

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Principali fonti di inquinamento Siti

• Aree agricole • Sito BP18 • Stagni

Sedimenti Cd Ni Cu Pb Cr Zn Hg

[mg/Kg] [mg/Kg] [mg/Kg] [mg/Kg] [mg/Kg] [mg/Kg] [mg/Kg]

1^stsampling 0,19 12,63 72,43 54,62 23,35 314,72 0,19

2^ndsampling 0,98 13,26 170,31 74,10 18,89 719,22 0,52

TEC 0,59 39,60 28,00 34,20 56,00 159,00 0,20

Acqua Cd Ni Cu Pb Cr Zn Hg

[μg/l] [μg/l] [μg/l] [μg/l] [μg/l] [μg/l] [μg/l]

1^stsampling 0,03 1,93 15,12 1,55 2,84 7,16 0,09

2^ndsampling 0,00 5,61 55,98 0,42 3,05 51,42 0,16

EQS 0,30 20,00 14,00 7,20 18,00 92,00 0,07

(25)

Principali fonti di inquinamento Siti

• Stagni

• Aree agricole

0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6

0 1 2 3 4 5 6 7 8 9

1 2 3 4 5 6 7 8 9 10

P-PO4 3-[mg/l]

N-NO3-[mg/l]

Sampling site N-NO3 P-PO43-

spring 1st pond village Cenetice 1st tributary 2nd tributary highway ring 3rd tributary 4th tributary Pruhonice g. highway runoff 5th tributary SWD Hotivar reservoir SWD CSO car repair shop SWD pipeline

0 1 2 3 4 5 6 7 8 9

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

N-NO3-[mg/l]

P-PO43-[mg/l]

Sampling site P-PO43- N-NO3