AIR AND WATER MANAGEMENT TECHNOLOGIES INTRODUCTION Workshop on Bioregenerative Life Support ISLSWG International Space Life Science Working Group 18 TH May 2015

Aero Sekur participation in the AGROSPACE sector Turin 18 TH May 2015 RecentZeolith

Main Characteristics Illumination: LED Substrate: Zeolith, Perlite Technique:Ebb & Flow Sensors:Soil Temperature, Wetting, PAR, PH, EC Cycle of Argula (36 days) Turin 18 TH May 2015

Aero Sekur participation in the AGROSPACE sector Turin 18 TH May 2015 Recent GreenMOSS Zeolith

GreenMOSS ATMOSPHERE MANAGEMENT SYSTEM INTERNAL THERMAL CONTROL SYSTEM PRIMARY STRUCTURE & SECONDARY STRUCTURE Turin 18 TH May 2015

Aero Sekur participation in the AGROSPACE sector Turin 18 TH May 2015 Recent GreenMOSS Zeolith Next Future Agrospace Conference 2016 EDEN ISS Test Laboratory

A Laboratory (4m x Ø2m) where to test air management systems, hydroponic water treatments and light systems, focused on space applications Turin 18 TH May 2015

Aero Sekur participation in the AGROSPACE sector Turin 18 TH May 2015 Recent GreenMOSS Zeolith Future Agrospace Conference 2016 EDEN ISS Test Laboratory PresentAir and Water management technologies (Contamination removal and Regenerable filtration)

Prof. Franco Cataldo Ing. Giuseppe Bonzano, Ing. Vittorio Rossetti and Ing. Lorenzo Fiore Torino, May 18, 2015 CNR-IMC ACTINIUM CHEMICAL RESEARCH

SUMMARY OF THE TOPICS  Regenerable air filtration  Photo-ozonolysis general mechanism of action  application to hydroponic water treatment  Understanding the chemical nature of silver biocide in flight water for ESA 10 CNR-IMC ACTINIUM CHEMICAL RESEARCH

AIR TREATMENT: POLLUTANTS REMOVAL IN A REGENERABLE FILTRATION SYSTEM 11 CNR-IMC ACTINIUM CHEMICAL RESEARCH

Regenerable air filtration system Aero Sekur working together with CNR-IMC and Actinium Chemical Research has patented a new and noteworthy technology for air filtration which is highly effective because: 1.It is suitable for the treatment of large air mass 2.It requires a low power consumption 3.The adsorbent bed is completely regenerable 4.The technology is suitable for military and space application See for example: US Patent 2012/ A1 filed Aug. 16, 2012 and assigned to Aero Sekur spa 12 CNR-IMC ACTINIUM CHEMICAL RESEARCH

The success of the new technology  The regenerable air filtration system in its simples version consists of a duct through which is flown in a laminar way a stream of contaminated air.  The walls of the duct are coated by the adsorbent materials which selectively remove the VOC from the contaminated air.  The device has been tested successfully in the VOC removal generated from the biochemical waste treatment system known as “MELISSA”.  It was also successfully tested in the removal of CWA and TIC 13 CNR-IMC ACTINIUM CHEMICAL RESEARCH

Examples of VOC successfully removed  Acetaldehyde  Simulant: Ethanol [Eth]  Dimethyl sulphide  Simulant: Carbon disulfide [Cds]  Benzene  Simulant: Toluene [Tol]  Furan  Simulant: Tetrahydrofuran [THF]  Isoprene  Simulant: 2-methyl-2-butene [2MBE]  N-methoxy, N-nitrosoamine and other amines  Simulant: Isopropylamine [Ispa] CNR-IMC ACTINIUM CHEMICAL RESEARCH

Adsorbent tested for the extraction system  Three different adsorbents were tested :  1) Activated Carbon Fibre (ACF-2000-AS) obtained by reduction at high temperature of a phenol-formaldehyde polymer. The fibre, in the form of a feltre, was charaterized by a surface area of 1,500 m 2 /g.  2) Multi Wall Carbon Nanotubes (MWCNTs).  3) Fullerene Black (FB)  A series tests were performed by passing 200 mL/min of N 2 containing water at 36-38% R.H. and 30 ppmv of total VOC. These experiments were aimed at assessing behavior of the adsorbent in humid gases.  They were performed in Frontal Gas Chromatography (FGC) that better simulates the conditions existing at the outlet of the waste treatment system. CNR-IMC ACTINIUM CHEMICAL RESEARCH

Extraction system geometry CNR-IMC ACTINIUM CHEMICAL RESEARCH

Selective Desorption with a reverse flow rate Desorption experiments performed under programmed temperature showed that a complete recovery of the 6 contaminants can be obtained when the diffusion-based filter is heated up to 550°C under a flow rate of an inert gas. The separation is such that some selectivity in the recovery is obtained. CNR-IMC ACTINIUM CHEMICAL RESEARCH

Fine tuning of the filter technical characteristics  Temperature:  Adsorption is improved with air at low temperatures ( ref. 5°C)  Desorption was made with :  Heating, till 500°C, settable at intermediate temperatures  Flow rate  Laminar type  Prototype tested flow rate till 1800 ml/h  Pressure  Flow laminar = pressure drop 0 psig  Vacuum at mbar for desorption CNR-IMC ACTINIUM CHEMICAL RESEARCH

Filter Modularity  Three filter container in parallel  Filtration, Regeneration, Stand by for safety redundance  Temperature control, on absorbtion and desorption phases  Pressure control, on absorbtion and desorption phases  Gas monitoring  Control system with signals input and signals and commands output CNR-IMC ACTINIUM CHEMICAL RESEARCH

PHOTO-OZONOLYSIS GENERAL MECHANISM OF ACTION 21 ACTINIUM CHEMICAL RESEARCH

Advanced water and wastewater treatment Aero Sekur working together with Actinium Chemical Research has patented another advanced technology for water and wastewater treatment which is highly effective because: 1.It is based on an advanced oxidation process 2.It employs the combined action of UV radiation and ozone 3.It is effective on heavy polluted waters like landfill leachate 4.It is suitable also for potabilization and sterilization of water See for example: US Patent US 2014/ A1 filed Oct. 9, 2014 and assigned to Actinium licensed to Aero Sekur spa 22 ACTINIUM CHEMICAL RESEARCH

Ozonolysis & photo-ozonolysis Step 1: O 3 + R 2 -C=C-R 2  2 R 2 C=O Selective Selective electrophilic addition of ozone on all available double bonds and degradation of the molecule in smaller products (see Scheme) Step 2: O 3 + hv  O 3 *  1 O 2 + O ( 1 D) O ( 1 D) + H 2 O  H 2 O 2 H 2 O 2 + hv  H 2 O 2 *  2 OH non-selective Ozone irradiated with UV ligh generates OH radicals which are very powerful non-selective oxidizing agents 23 ACTINIUM CHEMICAL RESEARCH

Oxidizing power of the OH radicals Oxidation potentials (Volt vs SHE)  Fluorine 3.06  Hydroxyl radical 2.80  Atomic oxygen 2.42  Ozone 2.08  H 2 O  ClO  Chlorine 1.36  O  ClO  HO▪ + H + + e -  H 2 O The oxidizing power of hydroxyl radical is very powerful. It is second only to fluorine and higher than ozone. 24 ACTINIUM CHEMICAL RESEARCH

Results on a landfill leachate wastewater Starting from a series of difficult samples of landfill leachate having : Initial COD Initial COD Final COD mg/L photo-ozonolysis 55 mg/L 5155 mg/L photo-ozonolysis 84 mg/L 3135 mg/L photo-ozonolysis 62 mg/L Pristine absorption Curve = dark After treatment = transparent ACTINIUM CHEMICAL RESEARCH

TREATMENT OF HYDROPONIC WATER SUPPLIED BY PROF. G. GIACOMELLI 26 ACTINIUM CHEMICAL RESEARCH

Ozonolysis and photo-ozonolysis of hydroponic water  Prof. Giacomelli from Tucson sent us a series of 14 water samples taken from his hydroponic plant in service.  The samples were composed by the classic Hoagland’s solution of micronutrients, were analyzed and subjected to ozonolysis or photo-ozonolysis.  The photo-ozonolysis was found very effective in reducing the COD level of the hydroponic water.  The photo-ozonolysis was found effective in the removal of root exudates which are undesired in multicrop systems. 27 ACTINIUM CHEMICAL RESEARCH

28 Results: Photo-ozonolysis more effective than ozonolysis in COD reduction of hydroponic water However the COD level of hydroponic water is not a problem and does not need such a treatment The ozonolysis and the photo-ozonolysis cause a pH reduction in hydroponic water ACTINIUM CHEMICAL RESEARCH

Photo-ozonolysis process is useful for the treatment of roots exudates  Roots exudates of certain species are toxic for other species  For multicrop hydroponic water it is necessary to remove the exudates  Photo-ozonolysis is effective in the decomposition of simple carboxylic acids (typical exudates) in a reasonable treatment time 29 ACTINIUM CHEMICAL RESEARCH

30 Photo-ozonolysis rate constants: Formic Acid: k = min -1 Oxalic Acid: k = min -1 Acetic Acid: k = min -1 ACTINIUM CHEMICAL RESEARCH

ON THE CHEMICAL NATURE OF COLLOIDAL SILVER IN FLIGHT WATER CNR-IMC ACTINIUM CHEMICAL RESEARCH

Silver as biocide in ISS drinking water We were commissioned by ESA to understand the chemical nature and reason of the biocide concentration fluctuation with time  Silver is used as biocide by ESA in ISS drinking water  Silver is added to water by an electrochemical process  Our study has shown that no metallic silver nanoparticles are present in flight water and sanification water  Our study has shown that all silver is in a ionic colloidal state 32 CNR-IMC ACTINIUM CHEMICAL RESEARCH

Colloidal metallic silver nanoparticles absorb at 400 nm Ag + reduction with: -NaBH 4 -Camelia Sinensis -Hibiscus Sabdariffa - γ Radiation surface plasmon resonance band (SPR) of metallic silver the surface plasmon resonance band (SPR) of metallic silver nanoparticles is observed at about 400 nm F. Cataldo et al., Eur. Chem. Bull. 2 (2013) F. Cataldo, Eur. Chem. Bull. 3 (2014) F. Cataldo, O. Ursini, G. Angelini, J. Radioanalytical Nuclear Chem. (2015) online CNR-IMC ACTINIUM CHEMICAL RESEARCH

34 What is the surface plasmon resonance (SPR) of silver nanoparticles? It is an electronic trasition at about 400 nm derived from the interation of light with the electron gas of each silver nanoparticles  No SPR?  No silver nanoparticles! CNR-IMC ACTINIUM CHEMICAL RESEARCH

Reduction of flight and sanification water to produce silver nanoparticles We have purposely added a reducing agent to cause the reduction of Ag + in any form it occurs to Ag° (metallic silver nanoparticles in colloidal state). Effective reducing agents tested:  Sodium Borohydride  Molecular hydrogen  Acetylene CNR-IMC ACTINIUM CHEMICAL RESEARCH

Flight water + NaBH 4 This is important ! Colloidal metalli silver is not detected by the S-C method CNR-IMC ACTINIUM CHEMICAL RESEARCH

Sanification water + NaBH 4 Initial growth of SPRB Decay in excess of reagent CNR-IMC ACTINIUM CHEMICAL RESEARCH

Nature of colloidal Ag + in flight water  The microparticle of the insoluble silver salt is surrounded by adsorbed ions and at higher distance by loosely bound couterions  The electrical double layer which is measured as Z- potential arises from the surface of adsorbed ions on the colloidal particle and the loosely bound counter-ions. A model of colloidal silver salt nanoparticle in colloidal state. CNR-IMC ACTINIUM CHEMICAL RESEARCH

THANK YOU FOR THE KIND ATTENTION ANY QUESTION? 39

APPENDIX 40

41 Typical composition & concentration of the Hoagland’s solution DaltonNutrient Stock solut. mol/LOPERATVE solution mol/LmM/Lmg/L 101.1KNO Ca(NO 3 ) KH 2 PO MgSO Ca(HPO 4 ) CaSO 4 2H 2 O K 2 SO Fe-EDDHA0.0192,897x H 3 BO ,626x MnCl 2 4H2O ,118x ZnSO 4 7H ,651x CuSO 4 5H2O ,204x H 2 MoO ,235x

42 Table - Analysis on Hydroponic Water Samples from Prof. G. Giacomelli UV spectra conductivityCODpHA 295 nmA 400 nm labelbottle #mS/cmmg/LpH nutrient solution LGH nutrient solution LGH0 bis (*)0.008 Net sample from mix blend Net sample from mix blend Net sample from mix blend Net sample from mix blend Net sample from mix blend Nutrient sample from mix blend Nutrient sample from mix blend Nutrient sample from mix blend Nutrient sample from mix blend Nutrient sample from mix blend Nutrient sample from mix blend Nutrient sample from mix blend Nutrient sample from mix blend Nutrient sample from mix blend (**) nm 292 nm

43 Photo-ozonolysis and ozonolysis effects on the Hoagland solutions Pre-UVUV+O 3 Post-UV COD minSample #ml solutsssmgO 3 mgO 3 /LmS/cmmg/LpHNotes No hv, only O No hv, only O No hv, only O No hv, only O

Search of SPRB in flight and sanification water The analysis of all the samples of flight and sanification water by electronic absorption spectroscopy has revealed that: 1.The SPRB of metallic silver is completely absent in all samples confirming the absence of metallic silver in colloidal state. 2.The baseline of all samples is not zero and this is in line with the presence of colloidal particles which cause light scattering

Flushing & Sanification: no Ag° Cataldo 0

Flushing water: no metallic silver  Brown line – absorption of pristine flight water. No SPR detected.  Green line – same as above after the addition of NaBH4. The SPRB band develops due to the formation of metallic silver.

ANALYSIS BY OF FLIGHT AND SANIFICATION WATER BY: DYNAMIC LIGHT SCATTERING (DLS) DETERMINATION OF Z- POTENTIAL

DLS used for measuring the size of colloidal particles in flight water Dynamic light scattering Dynamic light scattering It is a technique in chemical- physics that can be used to determine the size distribution profile of small particles in suspension or polymers in solution. [ ring]

DLS testing procedure  The DLS measurements were made on the instrument “Zetasizer Nano” from Malvern.  The samples were gently shaken before running the DLS and the results reported were taken in triplicate for each sample.  After 2h sedimentation, the samples were analyzed again by DLS in triplicate measuring this time only the smaller particles remained in suspension.

after shaking Avg particle size diameter by DLS taken after shaking Particles are very large not comparable with typical colloidal silver those measured in typical colloidal silver solutions where usually one can find values between 15 and 150 nm. [see F. Cataldo, Eur Chem Bull 3 (2014) 280] “Zero” is the flushing water with 0.5 mg/L of Ag + All the other samples are sanification water with approximately 10 mg/L Ag + DLS taken after shaking the solutions SAMPLE # Z-AVERAGE (Diameter nm) Polydispersion index ZERO OLD NEW OLD NEW

after 2h sedimentation Avg particle size diameter by DLS taken after 2h sedimentation Even after sedimentation, the colloidal typical colloidal silver solutions where usually one can find values between 15 and 150 nm. particles remain very large not comparable with those measured in typical colloidal silver solutions where usually one can find values between 15 and 150 nm. [see F. Cataldo, Eur Chem Bull 3 (2014) 280] “Zero” is the flushing water with 0.5 mg/L of Ag + All the other samples are sanification water with approximately 10 mg/L Ag + DLS taken after 2h sedimentation SAMPLE # Z-AVERAGE (Diameter nm) Polydispersion index ZERO OLD NEW OLD3893 (?)1 3NEW4424 (?)

Z-Potential of a colloidal solution Zeta potential is the potential difference between the dispersion medium and the stationary layer of fluid attached to the dispersed particle. [ Zeta potential [mV] Stability behavior of the colloid from 0 to ±5, Rapid coagulation or flocculation from ±10 to ±30Incipient instability from ±30 to ±40Moderate stability from ±40 to ±60Good stability more than ±61Excellent stability

Z-potential measured with DLS sample #Z-potential (mV)mS/cm zero+17, old-11, new-11, old-15, new-14, , Typical colloidal metallic silver solutions have a Z-potential in the range of -30 to -35 mV [see F. Cataldo, Eur Chem Bull 3 (2014) 280]. the values found suggest an intrinsically low colloidal stability. Thus, the values found suggest an intrinsically low colloidal stability. Z-potential measurements were made in triplicate using the DLS Zetasizer Nano from Malvern