Policy, legislation and advancedtreatment technologies for
industrial-environmental symbiosiswithin the Lagoon of Venice
Francesco Fatone
Laboratory of Bioprocess and Chemical-Environmental EngineeringDepartment of Biotechnology, University of Verona, Italy
Contents
• Porto Marghera: growth, potential tobecome Eco-Industrial Park and decline
• Lagoon of Venice: environmentalmanagement and focus on (waste)water
• Porto Marghera: focus on the petrochemicalwastewater treatment
• Final considerations…to stimulate thediscussion
Venice and Porto Marghera…within the Lagoon of Venice
Porto MargheraLarge Indutstrial Site
Venice historical centre
2000 hectares
History of and large industrial site, withina very fragile environmental context
• 1917: insufficient infrastructure in the old port ofVenice, new commercial port in the mainland
• 1917-1940: development of the 1st industrial area• 1955-1965: development and saturation of the 2nd
industrial area• 1965: planning of the 3rd industrial area• 1966: Venetian flood (194 cm) and booming of the
public concern about the environmentalmanagement of the Lagoon
Public perception(s) of the Lagoon
Venice historical city
Firms and employes in the industrial site
Firms
Employes
Sectors, firms and employes
Mannino et al., 2015
-
+
Industrial symbiosis
Industrial Symbiosis engagestraditionally separate industries in acollective approach to competitive
advantage involving physical sharingof materials, energy, water, and/or
by products
Certow, 2000
Conditions for the survival and thedevelopment of eco-industrial parks
• Synergies among the firms• Availability of infrastructure• Presence of a flexible regulatory
framework and favorable policies• Presence of information management
system
1998: Agreement for chemicalindustry in Porto Marghera -
aiming at the Eco-Industrial Park• Develop an environmental management systems
among the firms• Annual environmental accounting• Improve processes and develop research to this aim• Reduce and rationalize the use and transportation of
raw material• Replace the hazardous substances with less polluting
compounds
Industrial Symbiosis favourable factors forPorto Marghera industrial park in 2004
Mannino et al., 2015
Industrial symbiosis in the Porto Marghera site:immature and spontaneous, but effective
Mannino et al., 2015
Transition and decline of theindustrial symbiosis dream
Mannino et al., 2015
The unique case of the Lagoon of Venice
Main special national laws to protect and safeguardthe Lagoon form pollution:• Law 16 April 1973• Decree 24 Apr 1998• Decree 16 Dec 1998• Decree 09 Feb 1999• Decree 26 May 1999• Decree 30 Jul 1999
Regulation on non-conventional pollutants:the Lagoon of Venice as European precursor
Compound Limit for dischargeTotal PAHs, g/l 1Dioxins, pg/l (TE) 0.5Cyanides, g/l 5Arsenic, g/l 1Lead, g/l 10Cadmium, g/l 1Mercury, g/l 0.5PCB <Limit of DetectionTri-butyl-tin <Limit of DetectionOrgano-chlorine pesticides <Limit of Detection
Emission standards concerning 10 target compounds (law decree 30.07.99)
Study site: Industrial WWTP Porto Marghera, Venice, Italy
Porto Margherapetrochemical MBR
MBR-SG31
Clari-flocculation SG31
MBR-Pilot
PVDF HF Membrane 100 109 m2 Influent flowrate 45 720 m3/d
• Sampling period: from January 2006 to May 2008• Samples:
• Wastewater (25 samples):• WWTP Influent,• Effluent from Clariflocculation (CF effluent),• Effluent from MBR (MBR Effluent)
• Sewage sludge (5 samples, January-May 2008)• River water (25 samples) - Naviglio del Brenta (Oriago) river, a source of water supply for cooling
and different industrial processes in industrial site of Porto Marghera
FeSO4
Spent causticUp to pH 9.5-10
AnionicPolyelectrolyte
ClariflocculationEqualization
Sludgecollection tank
Thickening
Anoxic Aerobic
Pure oxygen
H2SO4Up to pH 7.5-8.5
Petrochemicalindustrialprocesses
Run-off
River
Dewatering
Incineration
Lago
on o
f Ven
ice
Sampling points
Sampling period and sampling points
PCBs in wastewater: DL-PCBsINFLUENT
• Out of 12 DL-PCBs, 6 detected• Penta-CB 105 (150 pg/L) and 118 (510 pg/L), and hexa-CB 156 and 167: 100 % FQ• Tetra-CB 77 and hepta-CB 189: FQ of 72% and 48%, respectively
MBR EFFLUENT• Only 2 PCBs > LOQ: 118 (40 pg/L, FQ 64 %) and 156 (30 pg/L, FQ 28 %)
OVERALL REMOVAL of ΣDL-PCB: 93 %• 90 % (PCB 118) – 100 % (PCB 189)
0
50
100
Primary Secondary Overall
156
Rem
oval
(%)
0
100
200
300
400
500
600
700
800
77 118 105 167 156 189
Con
cent
ratio
n of
PC
B-D
L (p
g/L)
0
50
100
Primary Secondary Overall
118
Rem
oval
(%)
118
0
50
100
Primary Secondary Overall
105
Rem
oval
(%)
105
Max
Min
Mdn
Q1
Q3
Inf EffPhCh EffMBR
Removal 1ry treatment
Removal 2ry treatmentOverall removal
156
• Toxicity equivalency factor (TEF) = the toxicity of PCBs relative to a reference compound - 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
• Total toxic equivalent (TEQ) = the sum of the products of the concentration of each compound multiplied by its TEF value and is an estimate
of the total TCDD–like activity of the mixture
World Health Organization (WHO) TEFs to calculate dioxin-like TEQ(WHO, 2005.) 0
0,01
0,02
0,03
0,04
0,05
0,06
WHO
-TEQ
mixt
ure
(pg
WHO
-TEQ
/L)
Dioxin-like PCBs
Homologs Congeners WHO-TEF 2005.
Tetra-CB PCB 77 0.0001Tetra-CB PCB 81 0.0003Penta-CB PCB 105 0.00003Penta-CB PCB 114 0.00003Penta-CB PCB 118 0.00003Penta-CB PCB 123 0.00003Penta-CB PCB 126 0.1Hexa-CB PCB 156 0.00003Hexa-CB PCB 157 0.00003Hexa-CB PCB 167 0.00003Hexa-CB PCB 169 0.03
Hepta-CB PCB 189 0.00003
80 % 95 %
75 %
Total dioxin–like activity: wastewater
TEQmixture = Σ(Ci × TEFi)
PCBs in wastewater: DL-PCBs
0.3 pgTEQ/L
0.0015 pgTEQ/L
FeSO4
Spent causticUp to pH 9.5-10
AnionicPolyelectrolyte
ClariflocculationEqualization
Sludgecollection tank
Thickening
Anoxic Aerobic
Pure oxygen
H2SO4Up to pH 7.5-8.5
Petrochemicalindustrialprocesses
Run-off
Dewatering
Incineration
Lago
on o
f Ven
iceINDUSTRIAL WWTP PORTO MARGHERA
River
19000 m3/h
1500 m3/h
ΣPCB 2.1 ng/L (1.0 – 4.4 ng/L)
ΣPCB 0.5 ng/L (0.2 – 1.1 ng/L)
ΣPCB mass flow rate:0.75 mg/h (0.3-1.7 mg/h)
ΣPCB mass flow rate:40 mg/h (19 - 84 mg/h)
Effluent
PCB (river) >> PCB (river)
! Total PCB mass flow rate of river has a more important impact on the Lagoon of Venice
than the WWTP effluent
PCBs in river vs. PCBs in WWTP effluent: mass flow rate
FeSO4
Spent causticUp to pH 9.5-10
AnionicPolyelectrolyte
ClariflocculationEqualization
Sludgecollection tank
Thickening
Anoxic Aerobic
Pure oxygen
H2SO4Up to pH 7.5-8.5
Petrochemicalindustrialprocesses
Run-off
Dewatering
Incineration
Lago
on o
f Ven
iceINDUSTRIAL WWTP PORTO MARGHERA
River
ΣPCB 2.1 ng/L (1.0 – 4.4 ng/L)
ΣPCB 0.5 ng/L (0.2 – 1.1 ng/L)
Effluent
WHO-TEQPCB (River) > WHO-TEQPCB (WWTP Effluent)
! Total DL-PCB in river has a more important impact on the Lagoon of Venice
than the WWTP effluent! The highest contribution to the total TEQ in both the river and the MBR effluent samples was observed
for mono-ortho-substituted PCB 118 (WHO-TEF of 0.00003)
PCBs in river vs. PCBs in WWTP effluent: TEQmixture
0.0015 pg WHO-TEQ/L(0.001 - 0.0141)
0.0053 pg WHO-TEQ/L(0.001 - 0.0337)
1 site and 3 types of wastewater
• Type A: Municipal wastewater TREATMENT ANDINDUSTRIAL REUSE
• Type B1 and B2: Industrial wastewaterTREATMENT AND DISCHARGE IN THE ADRIATICSEA
• Type B3: Groundwater from highly contaminatedsites TREATMENT AND DISCHARGE IN THEADRIATIC SEA
The flowratesDesign flowrate - WW Type A Dry weather average flowrate 4’600 m³/h Dry weather average flowrate 6’000 m³/h Peak wet flowrate 12’000 m³/h ( fitodepurazione)
Design flowrate - WW Type B WW B1 – average flowrate 2’300 m³/h WW B2 – average flowrate 700 m³/h Design average flowrate B1+B2 3’000 m³/h
WW B3 – average flowrate about 5’000 m³/d
Reuse
•FUSINA WWT Plant
WETLAND TREATMENT
Marine outfall
•MARGHERA WWT Plant
Type A wastewater
Type B1+B2 wastewater
Type B3 wastewater
Treated water to reuse
Sea outfall
SG31 SPM industrial WWTP
The full plan for wastewater treatment and reuse
MPPORTO
MARGHERA“B type” flowPre-treatment
Ca’ Solaro
Sile River
PIF
MoSAV(drinking water
supply)
“A type” flowpre-treatment
“A type” flowbiological treatment
“A type” flowPost-treatment
”B type” flowPost-treatment
“A type” flowfrom wetlands
Dischargeto sea
Watertreatmentand reusegeneral
plan
Integrated municipal-industrialwastewater treatment and reuse
Equalization
Clariflocculation
Post-denitrif.
WW B1+B2
Disin. & pump
Post-treatment
Constr. wetland
Tertiary treat.
CASP
UltraFiltration
Reverse Osmos.
Equal. & pump. Disin. & pump
Marine outfallIndustrial Reuse R1Industrial Reuse R2 DEMI
WW B0WW B0 WW B3
Reuse R1 ordischarge
If salinity <scaling
treshold
INTEGRATED PROJECT WW A
Municipal WWTP
Constructed wetland
The fullframework
LEGENDCollection wastewatertype ACollection wastewatertype B1+B2Collection wastewatertype B3Distribution treatedwaterMarine outfall pipe
LEGENDCollection wastewatertype ACollection wastewatertype B1+B2Collection wastewatertype B3Distribution treatedwaterMarine outfall pipe
Marineoutfall
Alcoa Enel F.
Enichem
Edison Az.EnelP.M.
Agip
PROGETTOINTEGRATOFUSINA
Constructed wetland120 hectares
Final considerationsThe industrial symbiosis in the large petrochemical area of
Porto Marghera spontanously triggered, but endogenous andexogenous social, legal and economic factors inhibited thedevelopment of the Eco-Industrial Park
The concentration of ubiquitous persistent compounds (e.g.PCBs) in industrial WW and sludge were lower than thosereported elsewhere, while the PCB loading of the river wasmore relevant than the treated industrial wastewater
The efforts to reach the environment-industry symbiosis shouldbe flexible with exogenous drivers of the industrial decisions
Thank you for your attention
Francesco Fatone
Laboratory of Bioprocess and Chemical-Environmental EngineeringDepartment of Biotechnology, University of Verona, Italy
Additional slides: sedimentsmanagement in the Lagoon of Venice
Chemical Class A Class B Class CAs 15 25 50Cd 1 5 20Cr 20 100 500Cu 40 50 400Hg 0.5 2 10Ni 45 50 150Pb 45 100 500Zn 200 400 3000Tot. Hydrocabons 30 500 4000Total PAHs 1 10 20PCBs 0.01 0.2 2Chlor. Pesticides 0.001 0.02 0.5Total PAHSs 1 10 20PCBs 0,01 0,02 2Chlor. Pesticides 0,001 0,02 0,5
