PRIN (National Interest Research Project)

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High salinity slops treatment through a biofilm-mbr inoculated with halophilic bacteria M. Torregrossa, G.Viviani, G. Mancini, D. Di Trapani, G. Di Bella, M. Capodici gmancini@dica.unict.

1 High salinity slops treatment through a biofilm-mbr inoculated with halophilic bacteria M. Torregrossa, G.Viviani, G. Mancini, D. Di Trapani, G. Di Bella, M. Capodici gmancini@dica.unict.it Giuseppe Mancini gmancini@dica.unict.it 1 IWA MTWR 2010 October 18-22, Istanbul PRIN (National Interest Research Project) This research is part of a national interest research program (PRIN), entitled: WATER BODIES PROTECTION FROM XENOBIOTC COMPOUNDS: NEW METHODS FOR THE ANALYSIS, THE CONTROL AND THE TREATMENT IN CIVIL AND INDUSTRIAL WASTEWATERS Participants are five research units belonging to different Universities: University of Catania, Polytechnic of Milan, University of Florence, University of Insubria (Como-Varese) and University of Naples Federico II. University of Palermo and Ferrara are also contributing to the research Giuseppe Mancini gmancini@dica.unict.it 2 IWA MTWR 2010 October 18-22, Istanbul ciao 1

Introduction Wastewaters contaminated by xenobiotics of oil-bearing origin,

environment create a major ecological problem throughout the world because

marine environment, the oil products transportation through sea is

spill out and of tank cleaning, slops, ballast and bilge waters being

2 Introduction Wastewaters contaminated by xenobiotics of oil-bearing origin, generated by various sources and subsequently discharged into the natural environment create a major ecological problem throughout the world because of the persistence and accumulation of these compounds. Giuseppe Mancini gmancini@dica.unict.it 3 IWA MTWR 2010 October 18-22, Istanbul Introduction With regards to marine environment, the oil products transportation through sea is considered the main cause of pollution, because of both accidental oily spill out and of tank cleaning, slops, ballast and bilge waters being discharged to the sea from oil tanker and other vessel typologies. Giuseppe Mancini gmancini@dica.unict.it 4 IWA MTWR 2010 October 18-22, Istanbul ciao 2

Introduction These issues are particularly critical in Mediterranean Sea that has been defined as a Special Area by the international Law MARPOL 73/78 (IMO,

Directive 2000/59/EC and 2005/35/EC put much further pressure on the collection by harbour authority. Giuseppe Mancini gmancini@dica.unict.

$Beside the presence of refractory compounds, these waters show extremely high salinity levels (up to 25.000 p.p.m.), that limit the possibility of discharge to sewers and address the disposal to the sea.$

3 Introduction These issues are particularly critical in Mediterranean Sea that has been defined as a Special Area by the international Law MARPOL 73/78 (IMO, 1973/1978) that strictly forbids any mineral oil or oily mixtures to be directly discharged to the sea by oil tankers. Directive 2000/59/EC and 2005/35/EC put much further pressure on the collection by harbour authority. Giuseppe Mancini gmancini@dica.unict.it 5 IWA MTWR 2010 October 18-22, Istanbul Introduction Slops are wash-waters originated from the cleaning of ships fuel tanks. Beside the presence of refractory compounds, these waters show extremely high salinity levels (up to p.p.m.), that limit the possibility of discharge to sewers and address the disposal to the sea. This severely lowers the concentrations limits for most of the sensible parameters, such both COD and xenobiotic hydrocarbons, thus requiring a higher level treatment. Giuseppe Mancini gmancini@dica.unict.it 6 IWA MTWR 2010 October 18-22, Istanbul ciao 3

Introduction Many of these fluids are very stable emulsion, which make conventional treatment difficult and normal separation processes alone (gravity,

2500 The most diffused 2000 1670 method for treatment of 1500 emulsified oily 1260 1310 1170 963 wastewater is deemulsification 1000 880 1055 1150 followed 718

chloride (mg/l) Ferric chloride plus 5 mg/l polyelectrolyte iron and alumina Trend of residual COD using ferric chloride plus 5 mg/l polyelectrolyte sulphates,

This is often achieved by granular activated carbon (GAC) filtration. Residual COD (mg/l) Giuseppe Mancini gmancini@dica.unict.

of wastewater of petrochemical origin with the advanced MBR process.

4 Introduction Many of these fluids are very stable emulsion, which make conventional treatment difficult and normal separation processes alone (gravity, flocculation, skimming) rarely effective The most diffused method for treatment of 1500 emulsified oily wastewater is deemulsification followed by clarification, which requires the use of a variety of chemicals such as sulphuric acid, Ferric chloride Ferric chloride (mg/l) Ferric chloride plus 5 mg/l polyelectrolyte iron and alumina Trend of residual COD using ferric chloride plus 5 mg/l polyelectrolyte sulphates, ect. The water phase from chemical treatment has to be further treated to meet today s effluent standard for discharge systems. This is often achieved by granular activated carbon (GAC) filtration. Residual COD (mg/l) Giuseppe Mancini gmancini@dica.unict.it 7 IWA MTWR 2010 October 18-22, Istanbul Introduction However GAC regeneration costs and tightening effluent regulations has generated interest in the treatment of wastewater of petrochemical origin with the advanced MBR process. Since free oil is inhibitory to these processes, the feed to biological treatment plants should, however, not contain more than typically 15 to 20 mg/l free oil. Higher SRT and TSS concentrations, compared to that of conventional activated sludge (CAS) processes, might lead to higher refractory hydrocarbons removal rate (Leiknes et al., 2006; Guo et al., 2007; Bouju et al., 2008) Giuseppe Mancini gmancini@dica.unict.it 8 IWA MTWR 2010 October 18-22, Istanbul ciao 4

Research Goals The normal bacteria which are growing in CAS and MBR cannot withstand at these adverse conditions, therefore it is necessary

, 2010) have dealt with this issue (adapting the microorganism) in MBR but still a lack of information is observed for applying MBR for high

The aim of this research was to investigate the performances of adapted microorganisms in a BF-MBR pilot plant in order to degrade the oils

The research has also led to a proper characterization of the specific wastewater as available scientific data are incomplete or too

5 Research Goals The normal bacteria which are growing in CAS and MBR cannot withstand at these adverse conditions, therefore it is necessary to be adapted (Lefebvre and Moletta, 2006). A few studies (Reid et al., 2006; Artiga et al., 2008; Llop et al., 2009; Soltani et al., 2010) have dealt with this issue (adapting the microorganism) in MBR but still a lack of information is observed for applying MBR for high salinity waters. The aim of this research was to investigate the performances of adapted microorganisms in a BF-MBR pilot plant in order to degrade the oils and other organic matters in very high salinity real wastewater of petrochemical origin (slops). The research has also led to a proper characterization of the specific wastewater as available scientific data are incomplete or too scattered. Giuseppe Mancini gmancini@dica.unict.it 9 IWA MTWR 2010 October 18-22, Istanbul Wastewater sampling and in situ pre-treatment Grab samples were collected from a floating tank of an oil costal deposit in the Augusta harbour (Sicily). Giuseppe Mancini gmancini@dica.unict.it 10 IWA MTWR 2010 October 18-22, Istanbul ciao 5

6 Wastewater sampling and in situ pre-treatment Giuseppe Mancini 11 IWA MTWR 2010 October 18-22, Istanbul Wastewater sampling and in situ pre-treatment Giuseppe Mancini 12 IWA MTWR 2010 October 18-22, Istanbul ciao 6

Lgs as 152/06) an indicator ph of the total organic - 7,5 contamination 5,5 9,5 throughout COD the prosecution mg/l of 1110 the < 160 Suspended Solids mg/l 26 < 80 experimental period, together with

7 Initial characterization of wastewater More than 800 liters of wastewater were pre-treated in situ and characterized. C10: 18,22mg/l C15: 25,29mg/l C20:7mg/l Measure Discharge l Total organic Parameter carbon Value Unit (TOC) was used D.Lgs as 152/06) an indicator ph of the total organic - 7,5 contamination 5,5 9,5 throughout COD the prosecution mg/l of 1110 the < 160 Suspended Solids mg/l 26 < 80 experimental period, together with and as a Total Dissolved control mg/l Solids of COD values, because of the uncertain reliability of the latter in very high salinity water. TPH mg/l 50 < 5 Al mg/l 0,044 < 2 As mg/l 0,096 < 0,5 Cd mg/l 0,019 < 0,02 Cr mg/l 0,042 < 2 Fe mg/l 0,1 < 2 Ni mg/l 0,066 < 2 Pb mg/l 0,024 < 0,2 Cu mg/l 0,006 < 0,1 Sn mg/l 0,001 < 10 Zn mg/l 0,034 < 0,5 Cl - 1 mg/l < 1200 * ph, TPH, TOC and COD, total suspended solid (TSS), total dissolved solid (TDS), chloride and conductivity in the feed, biological compartment and permeate were determined in accordance with Standard Methods (APHA, 2005). SO 4-2 mg/l 1970 < 1000 * Conductivity ms/cm 18,1 TOC mg/l 300 Giuseppe Mancini gmancini@dica.unict.it 13 IWA MTWR 2010 October 18-22, Istanbul First Respirometric batch experiments were carried out using a flowinggas/static-liquid type as batch respirometer (Spanjers et al., 1996). Tests were performed in order to investigate the feasibility of biological treatment for the high salinity slops Respirometric tests Giuseppe Mancini gmancini@dica.unict.it 14 IWA MTWR 2010 October 18-22, Istanbul ciao 7

First respirometric tests results Respirometric batch test of halophilic bacteria fed with slop Respirogram of acclimatized biomass from a CAS process with the addition of sodium acetate Giuseppe

it 15 IWA MTWR 2010 October 18-22, Istanbul Biological growth rate RAW CLARIFIED control R-Co-T0 1 C-Co-T0 25 at 27 C R-Co-T1 2 C-Co-T1 26 R-Co-T2 3 C-Co-T2 27 autoclaved with oxigen R-A+O -T0 4

(at 27 C) R+O -T2 9 C+O -T2 33 with oxigen e nutrient R+O+N-T0 10 C+O+N-T0 34 effect of oxigen and nutrient non the natural R+O+N-T1 11 C+O+N-T1 35 marine bacteria (at 27 C) R+O+N-T2 12 C+O+N-T2 36

8 First respirometric tests results Respirometric batch test of halophilic bacteria fed with slop Respirogram of acclimatized biomass from a CAS process with the addition of sodium acetate Giuseppe Mancini gmancini@dica.unict.it 15 IWA MTWR 2010 October 18-22, Istanbul Biological growth rate RAW CLARIFIED control R-Co-T0 1 C-Co-T0 25 at 27 C R-Co-T1 2 C-Co-T1 26 R-Co-T2 3 C-Co-T2 27 autoclaved with oxigen R-A+O -T0 4 C-A+O -T0 28 effect of only oxigen (at 27 C) R-A+O -T1 5 C-A+O -T1 29 R-A+O -T2 6 C-A+O -T2 30 with oxigen R+O -T0 7 C+O -T0 31 effect of oxigen non the natural R+O -T1 8 C+O -T1 32 marine bacteria (at 27 C) R+O -T2 9 C+O -T2 33 with oxigen e nutrient R+O+N-T0 10 C+O+N-T0 34 effect of oxigen and nutrient non the natural R+O+N-T1 11 C+O+N-T1 35 marine bacteria (at 27 C) R+O+N-T2 12 C+O+N-T2 36 autoclaved with Alcanivorax + R-A+O+N+Ax T0 13 C-A+O+N+Ax T0 37 oxigen+nutrient R-A+O+N+Ax T1 14 C-A+O+N+Ax T1 38 effect of only Alcanivorax (at 27 C) R-A+O+N+Ax T2 15 C-A+O +N+Ax T2 39 autoclaved with refinery sludge + R-A+O+N+Sr T0 16 C-A+O+N+Fg T0 40 oxigen + nutrient R-A+O+N+Sr T1 17 C-A+O+N+Fg T1 41 effect of only bacteria of refinery sludge (at 27 C) R-A +O+N+Sr T2 18 C-A+O+N+Fg T2 42 autoclaved with Halobacterium sp + R-A+O+N+Hl T0 19 C-A+O+N+Hl T0 43 oxigen+nutrient R-A+O+N+Hl T1 20 C-A+O+N+Hl T1 44 effect of only Halobacterium (a 37 C) R-A+O+N+Hl T2 21 C-A +O+N+Hl T2 45 with Alcanivorax + refinery sludge+ R+O+N+Ax+Sr T0 22 C+O+N+Ax+Fg T0 46 oxigen+nutrient R+O+N+Ax+Sr T1 23 C+O+N+Ax+Fg T1 47 effect of all bacteria: R+O+N+Ax+Sr T2 24 C+O+N+Ax+Fg T2 48 marine+alcanivorax+bacteriarefinery sludge (at 27 ) Giuseppe Mancini gmancini@dica.unict.it 16 IWA MTWR 2010 October 18-22, Istanbul ciao 8

9 Biological growth tests (TOC) Giuseppe Mancini 17 IWA MTWR 2010 October 18-22, Istanbul Biological growth tests (TOC-COD) Giuseppe Mancini 18 IWA MTWR 2010 October 18-22, Istanbul ciao 9

MBR bench scale plant The pilot process plant is was an hybrid feed with moving raw oily bed biofilm wastewater. reactor The(HMBBR) biological (Ødegaard phase was operated 2006; Germain insideeta al.

, 2010) towith allow a final at one ultrafiltration time the development stage, characterized of suspended by an hollow activated fibers sludge module, and biofilm in the following on free floating

10 MBR bench scale plant The pilot process plant is was an hybrid feed with moving raw oily bed biofilm wastewater. reactor The(HMBBR) biological (Ødegaard phase was operated 2006; Germain insideeta al. bench-scale 2007; Di Trapani reactoretdesigned al., 2010) towith allow a final at one ultrafiltration time the development stage, characterized of suspended by an hollow activated fibers sludge module, and biofilm in the following on free floating referredplastic to carriers BF-MBR followed (BioFilmby Membrane a submerged BioReactor) membrane (Leiknes unit asetsolid-liquid al., 2006; Sun separation et al., phase. 2009). BiofilmBio-Reactor Permeate Slops Mixed Storage carriers RAS Sludge UF-Membrane Air-blower Giuseppe Mancini gmancini@dica.unict.it 19 IWA MTWR 2010 October 18-22, Istanbul MBR bench scale plant The configuration was chosen in order to obtain higher performances with long minimum blocks and to enhance the degradation of refractory hydrocarbons. Moreover, biofilm, developed on the protected surface of the carrier, was supposed to reduce the influence of submicronic particles in the formation of fouling of the membrane, improving so the system effectiveness and extending the life of the membrane. Giuseppe Mancini gmancini@dica.unict.it 20 IWA MTWR 2010 October 18-22, Istanbul ciao 10

Membrane main characteristics Parameter Membranes type Value hollow fibers Module model ZeeWeed 01 (General ) Total membrane surface, (m 2 ) 0.

95 Suction period, (min) 4 Backwashing period, (min) 1 Giuseppe Mancini gmancini@dica.unict.

volume, (L) 30 Overall flow rate (L h -1 ) 1.

11 Membrane main characteristics Parameter Membranes type Value hollow fibers Module model ZeeWeed 01 (General ) Total membrane surface, (m 2 ) 0.1 Membrane pores size, (µm) 0.1 Trans-membrane pressure (TMP), (bar) Suction period, (min) 4 Backwashing period, (min) 1 Giuseppe Mancini gmancini@dica.unict.it 21 IWA MTWR 2010 October 18-22, Istanbul Parameter Carrier main characteristics and operating conditions Value Observation period (d) 22 Reactor volume, (L) 30 Overall flow rate (L h -1 ) 1.6 Hydraulic retention time, (h) 19 SRT, (d) 25 Suspended Carrier Kaldnes K1 Filling ratio, (%) 30 DO in the aerobic tank (mg/l) Recirculation flow ratio (L/h) 6 ph of the permeate 7.4 ± 0.6 MLSS (mg/l) Viscosity of mixed liquor (mpa s) Temperature ( C) 23.2 ± 0.5 Giuseppe Mancini gmancini@dica.unict.it 22 IWA MTWR 2010 October 18-22, Istanbul ciao 11

12 GELA Groundwater Treatment Plant as sludge source In order to exceed the greater obstacle to the biodegradation of hydrocarbons, that is the high salinity of waters (up to p.p.m.), the biological reactor was inoculated with activated sludge collected from the Gela refinery groundwater treatment plant where waters constantly show high salinity. Giuseppe Mancini 23 IWA MTWR 2010 October 18-22, Istanbul MBR bench scale plant Giuseppe Mancini 24 IWA MTWR 2010 October 18-22, Istanbul ciao 12

GELA Groundwater Treatment Plant as sludge source (University of Palermo) Although some problem of foaming

remove a large part of Total Organic Carbon. Giuseppe Mancini gmancini@dica.unict.

1,00 0,95 TOC (mg/l) 100 80 60 40 20 Washing 0,90 0,85 0,80 0,75 TMP (bar) 0 0,70 19/03 22/3 23/03 24/03 25/03

13 GELA Groundwater Treatment Plant as sludge source (University of Palermo) Although some problem of foaming raised during the first stages, the high SRT in the system and the membrane separation process allowed to remove a large part of Total Organic Carbon. Giuseppe Mancini gmancini@dica.unict.it 25 IWA MTWR 2010 October 18-22, Istanbul Influent and permeate TOC and TMP TOC raw TOC permeate TMP 1,00 0,95 TOC (mg/l) Washing 0,90 0,85 0,80 0,75 TMP (bar) 0 0,70 19/03 22/3 23/03 24/03 25/03 26/03 29/03 31/03 01/04 06/04 07/04 08/04 09/04 E TOC =91% Giuseppe Mancini gmancini@dica.unict.it 26 IWA MTWR 2010 October 18-22, Istanbul ciao 13

Influent and permeate TOC and TMP 140 120 TOC raw TOC permeate TMP 1,00 0,95 TOC (mg/l) 100 80 60 40 20 Washing 0,90 0,85 0,80 0,75 TMP (bar) 0 0,70 19/03 22/3 23/03 24/03 25/03 26/03 29/03 31/03

14 Influent and permeate TOC and TMP TOC raw TOC permeate TMP 1,00 0,95 TOC (mg/l) Washing 0,90 0,85 0,80 0,75 TMP (bar) 0 0,70 19/03 22/3 23/03 24/03 25/03 26/03 29/03 31/03 01/04 06/04 07/04 08/04 09/04 E TOC =91% Giuseppe Mancini gmancini@dica.unict.it 27 IWA MTWR 2010 October 18-22, Istanbul COD concentrations in the permeate % E COD =90% COD (mg/l) 100 Washing 95% 90% COD removal [%] 10 COD permeate COD raw COD removal E SST =72% 1 85% 19/03 22/3 23/03 24/03 25/03 26/03 29/03 31/03 01/04 06/04 07/04 08/04 09/04 SST = 19.9±2,3 Giuseppe Mancini gmancini@dica.unict.it 28 IWA MTWR 2010 October 18-22, Istanbul ciao 14

15 Morphology of the MBR sludge Sludge samples were observed under contrast-phase microscope with eyepiece magnification of x10 and objective magnification of x10 and x100. Pictures were taken by IM-50 Leica software.. Sessile ciliate Protozoa (Vorticella spp.) (a) (a) (b) Filamentous bacteria (Nostocoida limicola III )(b). Giuseppe Mancini 29 IWA MTWR 2010 October 18-22, Istanbul Conclusions The results of the reported short experimental campaign during which the pilot plant was directly fed with raw (and real) wastewater (without chemicalphyisical pre-treatment), showed: Respirometric activity of the biomass, previously acclimatized, has evidenced a not negligible ability to removal organic compound under high salinity conditions. The BF-MBR technology can be a reliable process to obtain high removal efficiencies for these waters The high sludge retention time and high filtration efficiency in the system enabled to remove a large part of TOC allowing to meet the limits imposed for discharge into the sea. Analysis of TMP trend however highlighted severe fouling problems due to the use of a no pretreated feed.. The presence of biofilm carriers into the system seemed to have no significant effects on the treatment performance. Some key remaining issues need to be addressed in application of the BF- MBR process to the treatment of slops including the reduction of membrane fouling as function of the needed pretreatment. Giuseppe Mancini gmancini@dica.unict.it 30 IWA MTWR 2010 October 18-22, Istanbul ciao 15

THANK YOU FOR YOUR KIND ATTENTION gmancini@dica.unict.it mtorre@idra.unipa.

16 THANK YOU FOR YOUR KIND ATTENTION This project was partially funded by the Italian Ministry of Education, University and Research (MIUR), through the program Research Program of Relevant National Interest, Fiscal year 2007 project 2007PM3TJM_002 (Project title: Water bodies protection from xenobioitc compounds: new methods for the analysis, the control and the treatment in civil and industrial wastewaters). Giuseppe Mancini 31 IWA MTWR 2010 October 18-22, Istanbul ciao 16

Small improvements in the treatment of oily wastes from marine transportation

University of Catania Department of Industrial Engineering Small improvements in the treatment of oily wastes from marine transportation IWWATV Athens May 21-23 2015 G. Mancini, M. Panzica, E. Palmeri,