Intervento di Petra Scanferla, CVR Conferenza Finale Progetto GREEN SITE: “Supercritical fluid technologies for river and sea dredge sediment remediation”. LIFE 10 ENV/IT/343. Venezia, 13 dicembre 2013

1. GREEN SITE
Action 4 – Technology assessment
CONSORZIO VENEZIA RICERCHE – dott. Petra Scanferla

2. Action 4 – Technology assessment
Sub – Action 4.1: Technical preparation (CVR)
Sub – Action 4.2: Evaluation (ALLES)
• AIM: assessing the prototype developed in order to investigate its
treatment efficacy of SFE and SCWO processes under real conditions with
selected contaminated soil and sediment samples.
• EXPECTED RESULTS:
clean-up (extraction) efficiency should be higher than 90% (SFE) and
over 90 % of efficiency in oxidation (SCWO) of target organic compounds;
improvement (by 30’-60’) of kinetic rates of extraction/oxidation of target
organic compounds;
end-products generated should be easily managed and discharged
without further expensive or complex treatment;
possibility to realize compact equipment, easy to transport and to install in
the intervention sites;
practical guidelines on optimal use of prototype.

3. Action 4 – Technology assessment
Starting points for the assessment
1. Definition of the target organic pollutants
A) characterizing the sediment contamination
of the forthcoming industrial channel that need
to be dredged…
“ISAP - Indagine sui sedimenti e sulle
acque dei canali di Porto Marghera e
delle aree lagunari antistanti”
MAV/CVN - ICRAM
Primarily: PAHs

4. Action 4 – Technology assessment
Starting points for the assessment
1. Definition of the target organic pollutants
A) characterizing the sediment contamination
of the forthcoming industrial channel that need
to be dredged…
B) characterizing the contaminated soil and
groundwater of the industrial area
Primarily PAHs than
amines and
organochlorine
PAHs

5. Action 4 – Technology assessment
Starting points for the assessment
Chemical
PAH:
50 and 100 mg/kg d.m.
As
Cd
Cr
Cu
Hg
Ni
Pb
Zn
Tot. Hydrocabons
Total PAHs
PCBs
Chlor.Pesticides
Class B
Class C
Class C+
mg/Kg d.w.
2. Definition of the concentration
levels of the selected
contaminants in the samples
that will be used for the
evaluation of process
performance.
Class A
mg/Kg d.w.
mg/Kg d.w.
mg/Kg d.w.
15
1
20
40
0.5
45
45
200
30
1
0.01
0.001
25
5
100
50
2
50
100
400
500
10
0.2
0.02
50
20
500
400
10
150
500
3000
4000
20
2
0.5
>50
>20
>500
>400
>10
>150
>500
>3000
>4000
>20
>2
>0.5
DISPOSAL SITES:
A,B,C: in lagoon
C+: no contact with lagoon

6. Action 4 – Technology assessment
Protocols and Procedures
A. Definition of procedures for the collection and preparation of ad
hoc sediment samples and extracts to be used for the evaluation
tests of the processes.
B. Identification of the matrices (solid, liquid and gaseous) that need
to be characterized during the tests.
C. Definition of protocols :
Starting run and blank test Protocol
Processes optimization Protocol

7. Action 4 – Technology assessment
A. Collection and preparation of ad hoc sediment samples
IPA
Naftalene
Acenaftilene
Acenaftene
Fluorene
Fenantrene
Antracene
Fluorantene
Pirene
Crisene
Benzo(a)antracene
Benzo(b+j)fluorantene
Benzo(k)fluorantene
Benzo(a)pirene
Benzo(e)pirene
Indeno(1,2,3-cd)pirene
Dibenzo(a,h)antracene
Benzo(g,h,i)perilene
IPA TOTALI
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
mg/Kg s.s.
1194.7
39.4
403.0
361.3
1452.4
230.6
565.5
335.8
233.6
212.6
186.5
116.2
134.7
117.6
52.4
64.5
78.9
5779.6
Idrocarburi totali
mg/Kg s.s.
13807

8. Action 4 – Technology assessment
A. Collection and preparation of ad hoc sediment samples
SAMPLE A
PAH ≈ 50 ppm
α
β
γ
m g/kg d.w .
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Fenentrene
Anthracene
Fluorantrene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b) fluoranthene
Benzo (k) fluoranthene
Benzo (j) fluoranthene
Benzo (e) pyrene
Benzo (a) pyrene
Perylene
Indeno (1,2,3-cd) Pyrene
Dibenzo (a, h) anthracene
Benzo (g, h, i) perylene
Dibenzo (a, i) pyrene
Dibenzo (a, e) pyrene
Dibenzo (a, l) pyrene
Dibenzo (a, h) pyrene
Total PAHs
Total hydrocarbons
1,900
0,540
4,700
8,900
14,700
1,750
8,700
5,400
1,730
1,490
1,100
0,480
0,540
0,700
0,940
0,272
0,490
0,161
0,470
0,049
0,047
0,076
0,012
55,0
53,0
1,800
0,430
3,800
5,600
13,100
1,580
8,200
4,800
1,660
1,390
1,030
0,570
0,440
0,670
0,910
0,263
0,460
0,152
0,450
0,045
0,046
0,071
0,013
48,0
48,2
Mean
conc.
st.dev.
SAMPLE B
PAH ≈ 75 ppm
α
1,700
0,457
4,000
6,400
13,367
1,667
8,033
4,800
1,737
1,500
1,100
0,520
0,527
0,710
0,960
0,278
0,500
0,165
0,487
0,049
0,050
0,080
0,013
49,3
54,4
γ
m g/kg d.w .
m g/kg d.w .
1,400
0,400
3,500
4,700
12,300
1,670
7,200
4,200
1,820
1,620
1,170
0,510
0,600
0,760
1,030
0,300
0,550
0,181
0,540
0,053
0,056
0,092
0,013
45,0
62,0
β
0,3
0,1
0,6
2,2
1,2
0,1
0,8
0,6
0,1
0,1
0,1
0,0
0,1
0,0
0,1
0,0
0,0
0,0
0,0
0,0
0,0
0,0
0,0
5,1
7,0
8 kg of sediment sample A
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Fenentrene
Anthracene
Fluorantrene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b) fluoranthene
Benzo (k) fluoranthene
Benzo (j) fluoranthene
Benzo (e) pyrene
Benzo (a) pyrene
Perylene
Indeno (1,2,3-cd) Pyrene
Dibenzo (a, h) anthracene
Benzo (g, h, i) perylene
Dibenzo (a, i) pyrene
Dibenzo (a, e) pyrene
Dibenzo (a, l) pyrene
Dibenzo (a, h) pyrene
Total PAHs
Total hydrocarbons
2,700
0,710
6,500
8,700
22,800
2,900
15,000
8,900
3,000
2,640
1,740
0,960
0,760
1,140
1,560
0,460
0,820
0,280
0,790
0,073
0,079
0,132
0,021
83,0
122,0
2,600
0,650
5,400
7,200
19,800
2,800
11,800
6,900
2,800
2,570
1,770
0,840
0,780
1,110
1,550
0,460
0,810
0,264
0,790
0,081
0,079
0,131
0,023
71,0
130,0
Mean
conc.
st.dev.
m g/kg d.w .
2,900
0,570
5,700
7,000
20,500
2,510
10,500
6,100
2,400
2,100
1,550
0,730
0,630
0,970
1,290
0,380
0,690
0,225
0,700
0,080
0,081
0,131
0,024
68,0
141,0
2,733
0,643
5,867
7,633
21,033
2,737
12,433
7,300
2,733
2,437
1,687
0,843
0,723
1,073
1,467
0,433
0,773
0,256
0,760
0,078
0,080
0,131
0,023
74,0
131,0
8 kg of sediment sample B
0,2
0,1
0,6
0,9
1,6
0,2
2,3
1,4
0,3
0,3
0,1
0,1
0,1
0,1
0,2
0,0
0,1
0,0
0,1
0,0
0,0
0,0
0,0
7,9
9,5

9. Action 4 – Technology assessment
B. Identification of the matrices : SFE
Sediment
sampling point
after SFE
Sampling points for SFE
Stocks/extracs
sampling point

10. Action 4 – Technology assessment
B. Identification of the matrices
Sediment
sampling point
after SFE
Sampling points for SFE
Stocks/extracs
sampling point

11. Action 4 – Technology assessment
C. Protocols realization
Sediment sampling
after SFE

12. Action 4 – Technology assessment
C. Protocols realization
Stocks/extracs sampling
after SFE

13. Action 4 – Technology assessment
B. Identification of the matrices : SCWO
Emissions
control
after
SCWO
Sampling points for SCWO
Liquid sample
control after
SCWO

14. Action 4 – Technology assessment
C. Protocols realization

15. Action 4 – Technology assessment
SFE results
1^ Test
Mean conc.
Sample
treated
m g/kg d.w .
PAH ≈ 50 ppm
2^ Test
m g/kg d.w .
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Fenentrene
Anthracene
Fluorantrene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b) fluoranthene
Benzo (k) fluoranthene
Benzo (j) fluoranthene
Benzo (e) pyrene
Benzo (a) pyrene
Perylene
Indeno (1,2,3-cd) Pyrene
Dibenzo (a, h) anthracene
Benzo (g, h, i) perylene
Dibenzo (a, i) pyrene
Dibenzo (a, e) pyrene
Dibenzo (a, l) pyrene
Dibenzo (a, h) pyrene
Total PAHs
Total hydrocarbons
1,700
0,457
4,000
6,400
13,367
1,667
8,033
4,800
1,737
1,500
1,100
0,520
0,527
0,710
0,960
0,278
0,500
0,165
0,487
0,049
0,050
0,080
0,013
49,3
54,4
Extraction
%
0,013
0,004
0,003
0,006
0,018
0,005
0,006
0,006
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
<0,001
0,061
8,900
90 min.
Sample
treated
3^ Test
Extraction
%
m g/kg d.w .
99,2
99,1
99,9
99,9
99,9
99,7
99,9
99,9
100,0
100,0
100,0
99,9
99,9
99,9
99,9
99,8
99,9
99,7
99,9
99,0
99,0
99,4
96,1
99,9
83,6
0,006
<0,001
0,003
0,012
0,076
0,008
0,094
0,062
0,007
0,012
0,009
0,004
0,004
0,007
0,003
0,001
0,004
0,001
0,005
<0,001
<0,001
<0,001
<0,001
0,320
<5
90 min.
Sample
treated
4^ Test
Extraction
%
m g/kg d.w .
99,6
99,9
99,9
99,8
99,4
99,5
98,8
98,7
99,6
99,2
99,2
99,2
99,2
99,0
99,7
99,6
99,2
99,4
99,0
99,0
99,0
99,4
96,1
99,4
95,4
0,051
<0,001
<0,001
<0,001
0,071
0,004
0,156
0,092
0,013
0,021
0,032
0,011
0,004
0,019
0,006
0,001
0,005
<0,001
0,010
<0,001
<0,001
<0,001
<0,001
0,490
5,000
60 min.
Sample
treated
Extraction
%
m g/kg d.w .
97,0
99,9
100,0
100,0
99,5
99,8
98,1
98,1
99,3
98,6
97,1
97,9
99,2
97,3
99,4
99,6
99,0
99,7
97,9
99,0
99,0
99,4
96,1
99,0
90,8
0,041
0,012
0,011
0,051
0,253
0,027
0,245
0,144
0,024
0,033
0,031
0,013
0,015
0,021
0,012
0,003
0,008
0,003
0,010
<0,001
0,002
0,002
<0,001
0,960
<5
60 min.
97,6
97,4
99,7
99,2
98,1
98,4
97,0
97,0
98,6
97,8
97,2
97,5
97,2
97,0
98,8
98,9
98,4
98,2
97,9
99,0
96,0
97,5
96,1
98,1
100,0

16. Action 4 – Technology assessment
SFE results
1^ Test
Mean conc.
m g/kg d.w .
PAH ≈ 75 ppm
Sample
treated
mg/kg d.w .
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Fenentrene
Anthracene
Fluorantrene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b) fluoranthene
Benzo (k) fluoranthene
Benzo (j) fluoranthene
Benzo (e) pyrene
Benzo (a) pyrene
Perylene
Indeno (1,2,3-cd) Pyrene
Dibenzo (a, h) anthracene
Benzo (g, h, i) perylene
Dibenzo (a, i) pyrene
Dibenzo (a, e) pyrene
Dibenzo (a, l) pyrene
Dibenzo (a, h) pyrene
Total PAHs
Total hydrocarbons
2,733
0,643
5,867
7,633
21,033
2,737
12,433
7,300
2,733
2,437
1,687
0,843
0,723
1,073
1,467
0,433
0,773
0,256
0,760
0,078
0,080
0,131
0,023
74,0
131,0
0,013
0,005
0,009
0,054
0,211
0,025
0,174
0,107
0,025
0,032
0,023
0,009
0,010
0,017
0,009
0,003
0,007
0,002
0,008
<0,001
<0,001
<0,001
<0,001
0,740
<5
Extraction
%
2^ Test
Sample
treated
3^ Test
Extraction
%
m g/kg d.w .
99,524
99,223
99,847
99,293
98,997
99,086
98,601
98,534
99,085
98,687
98,636
98,933
98,618
98,416
99,386
99,308
99,095
99,220
98,947
99,359
99,372
99,619
97,794
99,000
100,000
90 min.
0,068
0,010
0,023
0,087
0,170
0,016
0,320
0,207
0,034
0,046
0,056
0,024
0,021
0,039
0,019
0,006
0,015
0,004
0,019
<0,001
0,003
0,002
<0,001
1,190
6,700
90 min.
Sample
treated
4^ Test
Extraction
%
m g/kg d.w .
97,5
98,4
99,6
98,9
99,2
99,4
97,4
97,2
98,8
98,1
96,7
97,2
97,1
96,4
98,7
98,6
98,1
98,4
97,5
99,4
96,2
98,5
97,8
98,4
94,9
0,036
0,003
<0,001
<0,001
0,028
0,003
0,074
0,052
0,020
0,027
0,046
0,015
0,025
0,038
0,021
0,008
0,014
0,004
0,021
<0,001
0,001
0,001
<0,001
0,440
8,700
60 min.
Sample
treated
Extraction
%
m g/kg d.w .
98,7
99,5
100,0
100,0
99,9
99,9
99,4
99,3
99,3
98,9
97,3
98,2
96,5
96,5
98,6
98,2
98,2
98,4
97,2
99,4
98,7
99,2
97,8
99,4
93,4
0,041
0,011
0,022
0,098
0,380
0,039
0,300
0,186
0,032
0,045
0,030
0,012
0,017
0,023
0,014
0,004
0,011
0,004
0,014
<0,001
0,002
0,003
<0,001
1,290
16,100
60 min.
98,5
98,3
99,6
98,7
98,2
98,6
97,6
97,5
98,8
98,2
98,2
98,6
97,6
97,9
99,0
99,1
98,6
98,4
98,2
99,4
97,5
97,7
97,8
98,3
87,7

17. Action 4 – Technology assessment
SFE results
Σ PAH on the extracts from sample at 50 ppm
Σ PAH on the extracts from sample at 75 ppm

18. Action 4 – Technology assessment
SFE results
90%

19. Action 4 – Technology assessment
SFE results
C+
C
B
Class A
27 KWh
22 KWh

20. Action 4 – Technology assessment
SFE results
Capacity of SFE
pilot plant = 5 kg/h
B
Class A
27 KWh
22 KWh

21. Action 4 – Technology assessment
SCWO results
Extract treated in 50’:
14,35 Kg (~7% of organic contaminants)
Emission
limit
D.Lgs
152/2006
1st TEST
pH
Mineral oil
Conductivity
TDS
N nitrogen
Chlorides
Sulphates
Cu
Zn
mg/L
µS/cm
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
Liquid output
during the
Liquid output (discharge
during the
Blank sample - oxidation with
into
Contaminated Liquid before
isopropyl
oxidation with surface
DM water
Extract
flame ignition alcohol (7,5%)
extract
w ater)
6,45
5,98
6,00
4,58
2,59
<0,1
<0,1
5
68400
<0,1
18,3
63,8
29,5
343
<10
<10
<10
80
<0,1
<0,1
0,68
20
0,79
0,728
0,62
1200
11,1
0,75
21,6
1000
<0,01
<0,01
<0,01
0,4
0,323
<0,05
0,448
0,5
99,99 %

22. Action 4 – Technology assessment
SCWO results
Extract treated in 53’:
17,1 Kg (~7% of organic contaminants)
Emission
limit
D.Lgs
152/2006
2nd TEST
pH
Mineral oil
Conductivity
TDS
N nitrogen
Chlorides
Sulphates
Cu
Zn
Capacity of SCWO
pilot plant = 20 kg/h
mg/L
µS/cm
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
Liquid output
Liquid output (discharge
during the
during the
Blank sample - oxidation with
into
Contaminated Liquid before
isopropyl
oxidation with surface
DM water
Extract
flame ignition alcohol (7,5%)
extract
w ater)
6,45
6,14
5,65
3,71
2,21
<0,1
<0,1
5
66700
7,5
18,3
52,4
50,3
878
<10
<10
<10
80
0,87
20
0,139
<0,1
1,36
0,371
0,666
1200
5,26
5,15
93
1000
<0,01
<0,01
0,0136
0,4
2,74
0,43
0,394
0,5
99,99 %

23. Action 4 – Technology assessment
SCWO results
Air emission
during the
oxidation with
isopropyl
alcohol (7,5%)
2nd TEST
vapour water
TVOC
Air emission
during the
oxidation with
contaminated
extract
%
<1
8,4
Emission (com bustion
limit
plant w ith
D.Lgs
w aste
152/2006 incinerator)
<1
mg/Nmc
Emission
limit Dlgs
133/2005
9,3
O2
% v/v
9
4,7
CO2
% v/v
8,77
11,77
CO
mg/Nmc
156
14,2
100
NOx
mg/Nmc
<0,1
<0,1
200
SO2
mg/Nmc
4,2
1,5
200
single PAH congeners
ng/Nmc
<2
Σ PAH - upper bound
ng/Nmc
25
100.000
10.000
0,003
2,4
10.000
500.000
0,1
Σ PCDD+PCDF - upper bound ng/Nmc (I-TEQ)
ng/Nmc
Σ PCB - dioxin upper bound

24. Action 4 – Technology assessment
Conclusions
• EXPECTED RESULTS:
extraction efficiency should be higher than 90% (SFE) and
over 90 % of efficiency in oxidation (SCWO) of target
organic compounds;
improvement (by 30’-60’) of kinetic rates of
extraction/oxidation of target organic compounds;
end-products generated should be easily managed and
discharged without further expensive or complex treatment;
possibility to realize compact equipment, easy to transport
and to install in the intervention sites;
practical guidelines on optimal use of prototype

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