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Action 4 – Technology assessment
CONSORZIO VENEZIA RICERCHE – dott. Petra Scanferla
GREEN SITE
Action 4 – Technology assessment
Sub – Action 4.1: Technical preparation (CVR)Sub – Action 4.2: Evaluation (ALLES)
• 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.
• 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.
Action 4 – Technology assessment
1. Definition of the target organic pollutants
Starting points for the assessment
“ISAP - Indagine sui sedimenti e sulle acque dei canali di Porto Marghera e delle aree lagunari antistanti”MAV/CVN - ICRAM
A) characterizing the sediment contamination
of the forthcoming industrial channel that need to be dredged…
Primarily: PAHs
Action 4 – Technology assessment
1. Definition of the target organic pollutants
B) characterizing the contaminated soil and
groundwater of the industrial area
Primarily PAHs than
amines and
organochlorine
PAHs
A) characterizing the sediment contamination
of the forthcoming industrial channel that need to be dredged…
Starting points for the assessment
Action 4 – Technology assessment
2. Definition of the concentration
levels of the selected
contaminants in the samples
that will be used for the
evaluation of process
performance.
Chemical Class A Class B Class C Class C+
mg/Kg d.w. mg/Kg d.w. mg/Kg d.w. mg/Kg d.w.
As 15 25 50 >50
Cd 1 5 20 >20
Cr 20 100 500 >500
Cu 40 50 400 >400
Hg 0.5 2 10 >10
Ni 45 50 150 >150
Pb 45 100 500 >500
Zn 200 400 3000 >3000
Tot. Hydrocabons 30 500 4000 >4000
Total PAHs 1 10 20 >20
PCBs 0.01 0.2 2 >2
Chlor.Pesticides 0.001 0.02 0.5 >0.5
DISPOSAL SITES:
A,B,C: in lagoon
C+: no contact with lagoon
PAH:
50 and 100 mg/kg d.m.
Starting points for the assessment
Action 4 – Technology assessment
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
Protocols and Procedures
Action 4 – Technology assessment
A. Collection and preparation of ad hoc sediment samples
IPA Naftalene mg/Kg s.s. 1194.7 Acenaftilene mg/Kg s.s. 39.4 Acenaftene mg/Kg s.s. 403.0 Fluorene mg/Kg s.s. 361.3 Fenantrene mg/Kg s.s. 1452.4 Antracene mg/Kg s.s. 230.6 Fluorantene mg/Kg s.s. 565.5 Pirene mg/Kg s.s. 335.8 Crisene mg/Kg s.s. 233.6 Benzo(a)antracene mg/Kg s.s. 212.6 Benzo(b+j)fluorantene mg/Kg s.s. 186.5 Benzo(k)fluorantene mg/Kg s.s. 116.2 Benzo(a)pirene mg/Kg s.s. 134.7 Benzo(e)pirene mg/Kg s.s. 117.6 Indeno(1,2,3-cd)pirene mg/Kg s.s. 52.4 Dibenzo(a,h)antracene mg/Kg s.s. 64.5 Benzo(g,h,i)perilene mg/Kg s.s. 78.9 IPA TOTALI mg/Kg s.s. 5779.6 Idrocarburi totali mg/Kg s.s. 13807
Action 4 – Technology assessment
8 kg of sediment sample A 8 kg of sediment sample B
A. Collection and preparation of ad hoc sediment samples
SAMPLE A
PAH ≈ 50 ppm α β γ
Mean
conc. st.dev.
Naphthalene 1,900 1,800 1,400 1,700 0,3
Acenaphthylene 0,540 0,430 0,400 0,457 0,1
Acenaphthene 4,700 3,800 3,500 4,000 0,6
Fluorene 8,900 5,600 4,700 6,400 2,2
Fenentrene 14,700 13,100 12,300 13,367 1,2
Anthracene 1,750 1,580 1,670 1,667 0,1
Fluorantrene 8,700 8,200 7,200 8,033 0,8
Pyrene 5,400 4,800 4,200 4,800 0,6
Benzo (a) anthracene 1,730 1,660 1,820 1,737 0,1
Chrysene 1,490 1,390 1,620 1,500 0,1
Benzo (b) fluoranthene 1,100 1,030 1,170 1,100 0,1
Benzo (k) fluoranthene 0,480 0,570 0,510 0,520 0,0
Benzo (j) fluoranthene 0,540 0,440 0,600 0,527 0,1
Benzo (e) pyrene 0,700 0,670 0,760 0,710 0,0
Benzo (a) pyrene 0,940 0,910 1,030 0,960 0,1
Perylene 0,272 0,263 0,300 0,278 0,0
Indeno (1,2,3-cd) Pyrene 0,490 0,460 0,550 0,500 0,0
Dibenzo (a, h) anthracene 0,161 0,152 0,181 0,165 0,0
Benzo (g, h, i) perylene 0,470 0,450 0,540 0,487 0,0
Dibenzo (a, i) pyrene 0,049 0,045 0,053 0,049 0,0
Dibenzo (a, e) pyrene 0,047 0,046 0,056 0,050 0,0
Dibenzo (a, l) pyrene 0,076 0,071 0,092 0,080 0,0
Dibenzo (a, h) pyrene 0,012 0,013 0,013 0,013 0,0
Total PAHs 55,0 48,0 45,0 49,3 5,1
Total hydrocarbons 53,0 48,2 62,0 54,4 7,0
mg/kg d.w . mg/kg d.w .
SAMPLE B
PAH ≈ 75 ppm α β γ
Mean
conc. st.dev.
Naphthalene 2,700 2,600 2,900 2,733 0,2
Acenaphthylene 0,710 0,650 0,570 0,643 0,1
Acenaphthene 6,500 5,400 5,700 5,867 0,6
Fluorene 8,700 7,200 7,000 7,633 0,9
Fenentrene 22,800 19,800 20,500 21,033 1,6
Anthracene 2,900 2,800 2,510 2,737 0,2
Fluorantrene 15,000 11,800 10,500 12,433 2,3
Pyrene 8,900 6,900 6,100 7,300 1,4
Benzo (a) anthracene 3,000 2,800 2,400 2,733 0,3
Chrysene 2,640 2,570 2,100 2,437 0,3
Benzo (b) fluoranthene 1,740 1,770 1,550 1,687 0,1
Benzo (k) fluoranthene 0,960 0,840 0,730 0,843 0,1
Benzo (j) fluoranthene 0,760 0,780 0,630 0,723 0,1
Benzo (e) pyrene 1,140 1,110 0,970 1,073 0,1
Benzo (a) pyrene 1,560 1,550 1,290 1,467 0,2
Perylene 0,460 0,460 0,380 0,433 0,0
Indeno (1,2,3-cd) Pyrene 0,820 0,810 0,690 0,773 0,1
Dibenzo (a, h) anthracene 0,280 0,264 0,225 0,256 0,0
Benzo (g, h, i) perylene 0,790 0,790 0,700 0,760 0,1
Dibenzo (a, i) pyrene 0,073 0,081 0,080 0,078 0,0
Dibenzo (a, e) pyrene 0,079 0,079 0,081 0,080 0,0
Dibenzo (a, l) pyrene 0,132 0,131 0,131 0,131 0,0
Dibenzo (a, h) pyrene 0,021 0,023 0,024 0,023 0,0
Total PAHs 83,0 71,0 68,0 74,0 7,9
Total hydrocarbons 122,0 130,0 141,0 131,0 9,5
mg/kg d.w. mg/kg d.w .
Action 4 – Technology assessment
Sampling points for SFE
Stocks/extracs sampling point
Sediment sampling pointafter SFE
B. Identification of the matrices : SFE
Action 4 – Technology assessment
Sampling points for SFE
Stocks/extracs sampling point
Sediment sampling point after SFE
B. Identification of the matrices
Action 4 – Technology assessment
C. Protocols realization
Sediment sampling
after SFE
Action 4 – Technology assessment
Stocks/extracs sampling
after SFE
C. Protocols realization
Action 4 – Technology assessment
Emissions control after SCWO
Sampling points for SCWO
Liquid sample control after SCWO
B. Identification of the matrices : SCWO
Action 4 – Technology assessment
C. Protocols realization
Action 4 – Technology assessment
SFE results
PAH ≈ 50 ppm Mean conc.
Sample
treated
Extraction
%
Sample
treated
Extraction
%
Sample
treated
Extraction
%
Sample
treated
Extraction
%
mg/kg d.w . mg/kg d.w . mg/kg d.w . mg/kg d.w . mg/kg d.w .
Naphthalene 1,700 0,013 99,2 0,006 99,6 0,051 97,0 0,041 97,6
Acenaphthylene 0,457 0,004 99,1 <0,001 99,9 <0,001 99,9 0,012 97,4
Acenaphthene 4,000 0,003 99,9 0,003 99,9 <0,001 100,0 0,011 99,7
Fluorene 6,400 0,006 99,9 0,012 99,8 <0,001 100,0 0,051 99,2
Fenentrene 13,367 0,018 99,9 0,076 99,4 0,071 99,5 0,253 98,1
Anthracene 1,667 0,005 99,7 0,008 99,5 0,004 99,8 0,027 98,4
Fluorantrene 8,033 0,006 99,9 0,094 98,8 0,156 98,1 0,245 97,0
Pyrene 4,800 0,006 99,9 0,062 98,7 0,092 98,1 0,144 97,0
Benzo (a) anthracene 1,737 <0,001 100,0 0,007 99,6 0,013 99,3 0,024 98,6
Chrysene 1,500 <0,001 100,0 0,012 99,2 0,021 98,6 0,033 97,8
Benzo (b) fluoranthene 1,100 <0,001 100,0 0,009 99,2 0,032 97,1 0,031 97,2
Benzo (k) fluoranthene 0,520 <0,001 99,9 0,004 99,2 0,011 97,9 0,013 97,5
Benzo (j) fluoranthene 0,527 <0,001 99,9 0,004 99,2 0,004 99,2 0,015 97,2
Benzo (e) pyrene 0,710 <0,001 99,9 0,007 99,0 0,019 97,3 0,021 97,0
Benzo (a) pyrene 0,960 <0,001 99,9 0,003 99,7 0,006 99,4 0,012 98,8
Perylene 0,278 <0,001 99,8 0,001 99,6 0,001 99,6 0,003 98,9
Indeno (1,2,3-cd) Pyrene 0,500 <0,001 99,9 0,004 99,2 0,005 99,0 0,008 98,4
Dibenzo (a, h) anthracene 0,165 <0,001 99,7 0,001 99,4 <0,001 99,7 0,003 98,2
Benzo (g, h, i) perylene 0,487 <0,001 99,9 0,005 99,0 0,010 97,9 0,010 97,9
Dibenzo (a, i) pyrene 0,049 <0,001 99,0 <0,001 99,0 <0,001 99,0 <0,001 99,0
Dibenzo (a, e) pyrene 0,050 <0,001 99,0 <0,001 99,0 <0,001 99,0 0,002 96,0
Dibenzo (a, l) pyrene 0,080 <0,001 99,4 <0,001 99,4 <0,001 99,4 0,002 97,5
Dibenzo (a, h) pyrene 0,013 <0,001 96,1 <0,001 96,1 <0,001 96,1 <0,001 96,1
Total PAHs 49,3 0,061 99,9 0,320 99,4 0,490 99,0 0,960 98,1
Total hydrocarbons 54,4 8,900 83,6 <5 95,4 5,000 90,8 <5 100,0
1^ Test 2^ Test 3^ Test 4^ Test
90 min. 90 min. 60 min. 60 min.
Action 4 – Technology assessment
90 min. 90 min. 60 min. 60 min.
SFE results
PAH ≈ 75 ppm Mean conc.
Sample
treated
Extraction
%
Sample
treated
Extraction
%
Sample
treated
Extraction
%
Sample
treated
Extraction
%
mg/kg d.w. mg/kg d.w . mg/kg d.w. mg/kg d.w . mg/kg d.w.
Naphthalene 2,733 0,013 99,524 0,068 97,5 0,036 98,7 0,041 98,5
Acenaphthylene 0,643 0,005 99,223 0,010 98,4 0,003 99,5 0,011 98,3
Acenaphthene 5,867 0,009 99,847 0,023 99,6 <0,001 100,0 0,022 99,6
Fluorene 7,633 0,054 99,293 0,087 98,9 <0,001 100,0 0,098 98,7
Fenentrene 21,033 0,211 98,997 0,170 99,2 0,028 99,9 0,380 98,2
Anthracene 2,737 0,025 99,086 0,016 99,4 0,003 99,9 0,039 98,6
Fluorantrene 12,433 0,174 98,601 0,320 97,4 0,074 99,4 0,300 97,6
Pyrene 7,300 0,107 98,534 0,207 97,2 0,052 99,3 0,186 97,5
Benzo (a) anthracene 2,733 0,025 99,085 0,034 98,8 0,020 99,3 0,032 98,8
Chrysene 2,437 0,032 98,687 0,046 98,1 0,027 98,9 0,045 98,2
Benzo (b) fluoranthene 1,687 0,023 98,636 0,056 96,7 0,046 97,3 0,030 98,2
Benzo (k) fluoranthene 0,843 0,009 98,933 0,024 97,2 0,015 98,2 0,012 98,6
Benzo (j) fluoranthene 0,723 0,010 98,618 0,021 97,1 0,025 96,5 0,017 97,6
Benzo (e) pyrene 1,073 0,017 98,416 0,039 96,4 0,038 96,5 0,023 97,9
Benzo (a) pyrene 1,467 0,009 99,386 0,019 98,7 0,021 98,6 0,014 99,0
Perylene 0,433 0,003 99,308 0,006 98,6 0,008 98,2 0,004 99,1
Indeno (1,2,3-cd) Pyrene 0,773 0,007 99,095 0,015 98,1 0,014 98,2 0,011 98,6
Dibenzo (a, h) anthracene 0,256 0,002 99,220 0,004 98,4 0,004 98,4 0,004 98,4
Benzo (g, h, i) perylene 0,760 0,008 98,947 0,019 97,5 0,021 97,2 0,014 98,2
Dibenzo (a, i) pyrene 0,078 <0,001 99,359 <0,001 99,4 <0,001 99,4 <0,001 99,4
Dibenzo (a, e) pyrene 0,080 <0,001 99,372 0,003 96,2 0,001 98,7 0,002 97,5
Dibenzo (a, l) pyrene 0,131 <0,001 99,619 0,002 98,5 0,001 99,2 0,003 97,7
Dibenzo (a, h) pyrene 0,023 <0,001 97,794 <0,001 97,8 <0,001 97,8 <0,001 97,8
Total PAHs 74,0 0,740 99,000 1,190 98,4 0,440 99,4 1,290 98,3
Total hydrocarbons 131,0 <5 100,000 6,700 94,9 8,700 93,4 16,100 87,7
1^ Test 2^ Test 3^ Test 4^ Test
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
Action 4 – Technology assessment
SFE results
90%
SFE results
Action 4 – Technology assessment
C+
C
B
Class A22 KWh27 KWh
SFE results
Action 4 – Technology assessment
B
Class A
22 KWh27 KWh
Capacity of SFE
pilot plant = 5 kg/h
pH 6,45 5,98 6,00 4,58 2,59
Mineral oil mg/L 68400 <0,1 <0,1 <0,1 5
Conductivity µS/cm 18,3 63,8 29,5 343
TDS mg/L <10 <10 <10 80
N nitrogen mg/L <0,1 <0,1 0,68 20
Chlorides mg/L 0,79 0,728 0,62 1200
Sulphates mg/L 11,1 0,75 21,6 1000
Cu mg/L <0,01 <0,01 <0,01 0,4
Zn mg/L 0,323 <0,05 0,448 0,5
Contaminated
Extract
Blank sample -
Liquid before
flame ignition
Emission
limit
D.Lgs
152/2006 (discharge
into
surface
water)
1st TEST Liquid output
during the
oxidation with
isopropyl
alcohol (7,5%)
Liquid output
during the
oxidation with
extractDM water
Action 4 – Technology assessment
SCWO results
Extract treated in 50’:
14,35 Kg (~7% of organic contaminants)
99,99 %
pH 6,45 6,14 5,65 3,71 2,21
Mineral oil mg/L 66700 <0,1 <0,1 7,5 5
Conductivity µS/cm 18,3 52,4 50,3 878
TDS mg/L <10 <10 <10 80
N nitrogen mg/L 0,139 <0,1 0,87 20
Chlorides mg/L 1,36 0,371 0,666 1200
Sulphates mg/L 5,26 5,15 93 1000
Cu mg/L <0,01 <0,01 0,0136 0,4
Zn mg/L 2,74 0,43 0,394 0,5
DM water
Contaminated
Extract
Blank sample -
Liquid before
flame ignition
Emission
limit
D.Lgs
152/2006 (discharge
into
surface
water)
Liquid output
during the
oxidation with
isopropyl
alcohol (7,5%)
Liquid output
during the
oxidation with
extract
2nd TEST
Action 4 – Technology assessment
SCWO results
99,99 %
Extract treated in 53’:
17,1 Kg (~7% of organic contaminants)
Capacity of SCWO
pilot plant = 20 kg/h
vapour water % <1 <1
TVOC mg/Nmc 8,4 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
Σ PCDD+PCDF - upper bound ng/Nmc (I-TEQ) 0,003 10.000 0,1
Σ PCB - dioxin upper bound ng/Nmc 2,4 500.000
Air emission
during the
oxidation with
isopropyl
alcohol (7,5%)
Air emission
during the
oxidation with
contaminated
extract
2nd TEST
Emission
limit Dlgs
133/2005 (combustion
plant w ith
w aste
incinerator)
Emission
limit
D.Lgs
152/2006
Action 4 – Technology assessment
SCWO results
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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