Green Site Project results

Action 4 – Technology assessment

CONSORZIO VENEZIA RICERCHE – dott. Petra Scanferla

GREEN SITE

Action 4 – Technology assessmentSub – 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.


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: PAHsPrimarily: PAHs


1. Definition of the target organic pollutants

B) characterizing the contaminated soil and groundwater of the industrial area

Primarily PAHs than Primarily PAHs than amines and amines and organochlorineorganochlorine

PAHsA) characterizing the sediment contamination of the forthcoming industrial channel that need to be dredged…



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 >50Cd 1 5 20 >20Cr 20 100 500 >500Cu 40 50 400 >400Hg 0.5 2 10 >10Ni 45 50 150 >150Pb 45 100 500 >500Zn 200 400 3000 >3000Tot. Hydrocabons 30 500 4000 >4000Total PAHs 1 10 20 >20PCBs 0.01 0.2 2 >2Chlor.Pesticides 0.001 0.02 0.5 >0.5

DISPOSAL SITES:A,B,C: in lagoonC+: no contact with lagoon

PAH: PAH: 50 and 100 mg/kg d.m.50 and 100 mg/kg d.m.



A. Definition of procedures for the collection and preparation of ad hoc sediment samples 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


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


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

mg/kg d.w . mg/kg d.w .


Sampling points for SFE

Stocks/extracs sampling point

Sediment sampling pointafter SFE

B. Identification of the matrices : SFE


Sampling points for SFE

Stocks/extracs sampling point

Sediment sampling point after SFE

B. Identification of the matrices

Action 4 – Technology assessmentC. Protocols realization

Sediment sampling after SFE


Stocks/extracs sampling after SFE

C. Protocols realization


Emissions control after SCWO

Sampling points for SCWO

Liquid sample control after SCWO

B. Identification of the matrices : SCWO

Action 4 – Technology assessmentC. 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 97,6Acenaphthylene 0,457 0,004 99,1 <0,001 99,9 <0,001 99,9 0,012 97,4Acenaphthene 4,000 0,003 99,9 0,003 99,9 <0,001 100,0 0,011 99,7Fluorene 6,400 0,006 99,9 0,012 99,8 <0,001 100,0 0,051 99,2Fenentrene 13,367 0,018 99,9 0,076 99,4 0,071 99,5 0,253 98,1Anthracene 1,667 0,005 99,7 0,008 99,5 0,004 99,8 0,027 98,4Fluorantrene 8,033 0,006 99,9 0,094 98,8 0,156 98,1 0,245 97,0Pyrene 4,800 0,006 99,9 0,062 98,7 0,092 98,1 0,144 97,0Benzo (a) anthracene 1,737 <0,001 100,0 0,007 99,6 0,013 99,3 0,024 98,6Chrysene 1,500 <0,001 100,0 0,012 99,2 0,021 98,6 0,033 97,8Benzo (b) fluoranthene 1,100 <0,001 100,0 0,009 99,2 0,032 97,1 0,031 97,2Benzo (k) fluoranthene 0,520 <0,001 99,9 0,004 99,2 0,011 97,9 0,013 97,5Benzo (j) fluoranthene 0,527 <0,001 99,9 0,004 99,2 0,004 99,2 0,015 97,2Benzo (e) pyrene 0,710 <0,001 99,9 0,007 99,0 0,019 97,3 0,021 97,0Benzo (a) pyrene 0,960 <0,001 99,9 0,003 99,7 0,006 99,4 0,012 98,8Perylene 0,278 <0,001 99,8 0,001 99,6 0,001 99,6 0,003 98,9Indeno (1,2,3-cd) Pyrene 0,500 <0,001 99,9 0,004 99,2 0,005 99,0 0,008 98,4Dibenzo (a, h) anthracene 0,165 <0,001 99,7 0,001 99,4 <0,001 99,7 0,003 98,2Benzo (g, h, i) perylene 0,487 <0,001 99,9 0,005 99,0 0,010 97,9 0,010 97,9Dibenzo (a, i) pyrene 0,049 <0,001 99,0 <0,001 99,0 <0,001 99,0 <0,001 99,0Dibenzo (a, e) pyrene 0,050 <0,001 99,0 <0,001 99,0 <0,001 99,0 0,002 96,0Dibenzo (a, l) pyrene 0,080 <0,001 99,4 <0,001 99,4 <0,001 99,4 0,002 97,5Dibenzo (a, h) pyrene 0,013 <0,001 96,1 <0,001 96,1 <0,001 96,1 <0,001 96,1Total PAHs 49,3 0,061 99,9 0,320 99,4 0,490 99,0 0,960 98,1Total 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.


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 98,5Acenaphthylene 0,643 0,005 99,223 0,010 98,4 0,003 99,5 0,011 98,3Acenaphthene 5,867 0,009 99,847 0,023 99,6 <0,001 100,0 0,022 99,6Fluorene 7,633 0,054 99,293 0,087 98,9 <0,001 100,0 0,098 98,7Fenentrene 21,033 0,211 98,997 0,170 99,2 0,028 99,9 0,380 98,2Anthracene 2,737 0,025 99,086 0,016 99,4 0,003 99,9 0,039 98,6Fluorantrene 12,433 0,174 98,601 0,320 97,4 0,074 99,4 0,300 97,6Pyrene 7,300 0,107 98,534 0,207 97,2 0,052 99,3 0,186 97,5Benzo (a) anthracene 2,733 0,025 99,085 0,034 98,8 0,020 99,3 0,032 98,8Chrysene 2,437 0,032 98,687 0,046 98,1 0,027 98,9 0,045 98,2Benzo (b) fluoranthene 1,687 0,023 98,636 0,056 96,7 0,046 97,3 0,030 98,2Benzo (k) fluoranthene 0,843 0,009 98,933 0,024 97,2 0,015 98,2 0,012 98,6Benzo (j) fluoranthene 0,723 0,010 98,618 0,021 97,1 0,025 96,5 0,017 97,6Benzo (e) pyrene 1,073 0,017 98,416 0,039 96,4 0,038 96,5 0,023 97,9Benzo (a) pyrene 1,467 0,009 99,386 0,019 98,7 0,021 98,6 0,014 99,0Perylene 0,433 0,003 99,308 0,006 98,6 0,008 98,2 0,004 99,1Indeno (1,2,3-cd) Pyrene 0,773 0,007 99,095 0,015 98,1 0,014 98,2 0,011 98,6Dibenzo (a, h) anthracene 0,256 0,002 99,220 0,004 98,4 0,004 98,4 0,004 98,4Benzo (g, h, i) perylene 0,760 0,008 98,947 0,019 97,5 0,021 97,2 0,014 98,2Dibenzo (a, i) pyrene 0,078 <0,001 99,359 <0,001 99,4 <0,001 99,4 <0,001 99,4Dibenzo (a, e) pyrene 0,080 <0,001 99,372 0,003 96,2 0,001 98,7 0,002 97,5Dibenzo (a, l) pyrene 0,131 <0,001 99,619 0,002 98,5 0,001 99,2 0,003 97,7Dibenzo (a, h) pyrene 0,023 <0,001 97,794 <0,001 97,8 <0,001 97,8 <0,001 97,8Total PAHs 74,0 0,740 99,000 1,190 98,4 0,440 99,4 1,290 98,3Total 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


Σ PAH on the extracts from sample at 50 ppm

Σ PAH on the extracts from sample at 75 ppm


90%

SFE results


C+

C

B

Class A22 KWh27 KWh

SFE results


B

Class A

22 KWh27 KWh

Capacity of SFE pilot plant = 5 kg/h5 kg/h

pH 6,45 5,98 6,00 4,58 2,59Mineral oil mg/L 68400 <0,1 <0,1 <0,1 5Conductivity µS/cm 18,3 63,8 29,5 343TDS mg/L <10 <10 <10 80N nitrogen mg/L <0,1 <0,1 0,68 20Chlorides mg/L 0,79 0,728 0,62 1200Sulphates mg/L 11,1 0,75 21,6 1000Cu mg/L <0,01 <0,01 <0,01 0,4Zn 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 2,21Mineral oil mg/L 66700 <0,1 <0,1 7,5 5Conductivity µS/cm 18,3 52,4 50,3 878TDS mg/L <10 <10 <10 80N nitrogen mg/L 0,139 <0,1 0,87 20Chlorides mg/L 1,36 0,371 0,666 1200Sulphates mg/L 5,26 5,15 93 1000Cu mg/L <0,01 <0,01 0,0136 0,4Zn mg/L 2,74 0,43 0,394 0,5

DM waterContaminated

Extract

Blank sample - Liquid before flame ignition

Emission limit

D.Lgs 152/2006 (discharge

into surface water)



alcohol (7,5%)


oxidation with extract

2nd TEST


99,99 %

Extract treated in 53’:17,1 Kg (~7% of organic contaminants)

Capacity of SCWO pilot plant = 20 kg/h20 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 0,1Σ PCB - dioxin upper bound ng/Nmc 2,4 500.000

Air emission during the


alcohol (7,5%)

Air emission during the

oxidation with contaminated

extract

2nd TEST

Emission limit Dlgs 133/2005

(combustion plant w ith

waste incinerator)

Emission limit D.Lgs

152/2006


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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GRAZIE PER L’ATTENZIONEContatto: [email protected]

Date post:	13-Jul-2015
Category:	Technology
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