Project Partners and Institutions:

Project Director:

CS II.Dr.eng. Tanta-Verona IORDACHE, Vice-leader of Advanced Polymer Materials and Polymer Recycling Group, Polymers Department, iordachev.icechim@gmail.com

Coordinator:

National Research & Development Institute for Chemistry and Petrochemistry-ICECHIM, Bucharest, Romania (www.icechim.ro);

Project Responsible: 

CS II.Dr.eng. Carmen-Eugenia SIRBU, Head of Agrochemical and plant nutrition laboratory, Department of Researches in Soil Sciences, Agrochemical and Environmental Protection, carmene.sirbu@yahoo.ro

Prof. Dr.eng. Francois Xavier PERRIN, Professor at MAPIEM Laboratory,    perrin@univ-tln.fr

Prof. Dr.eng. Artur José Monteiro VALENTE, Sub-director of the Chemistry Department, avalente@qui.uc.pt

Partners:

National Research & Development Institute for Soil Sciences, Agrochemistry and Environment - ICPA, Bucharest, Romania (https://www.icpa.ro);

University of Toulon-MAPIEM Laboratory, Toulon, France (http://mapiem.univ-tln.fr);

University of Coimbra, Coimbra, Portugal (https://www.uc.pt/en);

Unitatea executiva pentru finantarea invatamantului superior, a cercetarii, dezvoltarii  si inovarii (UEFISCDI): https://www.uefiscdi.ro/

UEFISCDI contract no. 39 ⁄ 2017; UEFISCDI Contract budget: 250,027.00 €

Fundação para a Ciência e a Tecnologia (FCT): http://www.fct.pt/

FTC: 66,441.06 €

L'Agence nationale de la recherche (ANR): http://www.agence-nationale-recherche.fr/

ANR: 236,000.00 € 

The need for innovative strategies for water and soil protection that substitute the time-, energy- and resource-consuming remediation processes with other more efficient and environmentally-friendly is becoming urgent. In this respect, the interest of this project is to promote such solutions for public and private practitioners and to up-rise industrial competitiveness through economically sustainable technologies/products, in the Agriculture Field and indirectly in the Water Management aria. Therefore, this project practically develops protective composite layers (as end-products) with high efficiency towards pollution of underground water and soil, but without affecting the plants growth. ProWsper is an experimental and demonstrative research project conducted in partnership with four prestigious Institutions, from three European countries (Romania, France and Portugal) that face these common problems. In order to succeed, the implementation gap from Prototyping to Marketing and thereafter to practitioners will be narrowed by social/industrial awareness campaigns using various channels

Develop original, sustainable, and cost-effective solutions/products for protecting underground water and soil against nutrient and pesticide pollution while ensuring the well-balanced growth of plants (particularly, for greenhouses and small crop cultures). Applying such solutions/products during the fruit/vegetable growth cycles, reduces pollution and provides humid- and nutrient-stable environment for plant growth.

(i) 6 ISI Peer-reviewed OA Papers sent for publication in prestigious journals, (ii) 2 international conference or symposia papers per calendar year, (iii) two national Patent applications and one European Patent applications; (iv) participation to seminars and innovation salons; (v) organisation of workshops and construction of the ProWsper website dedicated to rising awareness of the project scope, objective and results.

Team Staff from INCDCP-ICECHIM

Team Staff from INCDCP-ICPA

Team Staff from MAPIEM Laboratory

Team Staff from the University of Coimbra

  Project Partners would like to thank the EU and (UEFISCDI, ANR and FTC) for funding, in the frame of the collaborative international consortium (ProWsper) financed under the ERA-NET Cofund WaterWorks2015 Call. This ERA-NET is an integral part of the 2016 Joint Activities developed by the Water Challenges for a Changing World Joint Programme Initiative (Water JPI) http://www.waterjpi.eu

Sumar etapa I:

Etapa I / 2017

Titlu: Prepararea particulelor hibride pentru retentia/eliberarea de pesticide si nutrienti organici

Perioada: 14/06/2017 - 31/12/2017

Raportul de cercetare corepunzator etapei 1/2017 si-a propus urmatoarele obiective:

• (INCDCP-ICECHIM Bucuresti) - Sinteza particulelor de silicat modificat pentru retentia/eliberarea de pesticide prin polimerizarea gazda-oaspete a monomerilor vinilici si caracterizarea fizico-chimica a materialelor hibride. Astfel pentru indeplinirea obiectivului s-au parcurs urm?toarele etape: Ob?inerea unor noi silicati modificati prin procedeul de imprentare moleculara gazda-oaspete care consta in polimerizarea radicalica a acrilonitrilului (AN) sau a unei solutii de AN si pesticid (Dithane M-45) in porii unui zeolit mezoporos (perlit expandat); Caracterizarea matricei anorganice utilizate la obtinerea hibridelor modificate dar si a silicatilor sintetizati cu ajutorul tehnicilor urmatoare in scopul obtinerii informatiilor privind: compozi?ie chimica (FTIR), dimensiuni particule si potential Zeta (DLS), structura chimica (XRD), analiza microstructurala (SEM), proprietati texturale (BET).
• Prepararea particulelor de hidrogel/celuloza bateriana prin polimerizare in solutie pentru retentia/eliberarea de nutrienti organici si caracterizare fizico-chimica a hidrogelurilor sintetizate. Acest obiectiv a fost indeplinit prin sinteza unor particule de hidrogeluri compozite pe baza de celuloza bateriana si acid poliacrilc reticulat cu N,N’- metilenbisacrilamida printr-o reactie de copolimerizare radicalica reticulanta a acidului acrilic cu N,N’-bismetilenacrilamida, initiata de un sistem redox format din persulfatul de potasiu (KPS) si metabisulfitul de sodiu (MS), in apa distilata, in prezenta de celuloza bateriana. Hidrogelurile compozite astfel obtinute au fost caracterizate in scopul determinarii influentei variatiei concentratiei de reactanti, asupra gradului de gonflare (absorbtiei de apa). De asemenea, noile structuri de hidrogel compozit au fost caracterizate si fizico-chimic prin spectroscopie FTIR, prin analize TGA/DTG si prin microscopie electronica de baleaj SEM.
• (ICPA Bucuresti) - Stabilirea pesticidelor tinta si a tipurilor de culturi si de soluri pentru utilizarea hibridelor compozite si caracterizarea dinamica a materiilor prime, a particulelor de silicat modificatsi a particulelor de hidrogel/ bioceluloza. Realizarea obiectivului s-a facut prin analiza unei game largi de compu?i activi si substan?e comerciale omologate, principalele criterii de selectie constand in modul de aplicare si caile de ac?iune, culturile la care se pot aplica, tipul de patogeni asupra c?rora ac?ioneaz?. Pentru aceasta a fost elaborata schema experimentala de retinere in regim dinamic a compusului mancozeb din pesticidul Dithane M-45, precum si determinarea capacitatii de absortie in regim dinamic a substantelor organice. 

Rezultate etapa I:

In cadrul acestei etape au efectuate 3 deplasari in strainatate ce au avut ca scop diseminarea rezultatelor prin intemediul comunicarilor (doua comunicari) in cadrul conferintelor si activitati de networking (ce include si perspective de colaborare& noutati pentru proiect) prin intermediul intalnirii de Kick-off al Proiectelor finantate prin programul Cofund ERANET WaterWorks2015 diseminat pe site-ul www.waterjpi.eu. O deplasare in tara a fost efectuata in cadrul Conferintei Internationale PRIOCHEM, organizata de catre INCDCP-ICECHIM pentru comunicarea rezultatelor cercetarilor sub forma unei comunicari tip Poster. In cadrul conferintei PRIOCHEM am stabilit colaborari bilaterale in domeniul Polimerilor Imprentati Molecular cu o Universitate din UK (Medway School of Pharmacy, University of Kent, Prof. Dr. Andrew Hall).

In cadrul WorkShop-ului organizat la ICECHIM Bucruresti au fost prezenti Responsabilii de Proiect, i.e. Dr. ing. Carmen Sirbu; Prof.Dr. Xavier Perrin si Prof. Dr. Artur Valente, din Organizatiile Partenere Nationale-INCDPAPM ICPA si respectiv Internationale- MAPIEM Lab., TOULON, FRANTA si UNIVERSITATEA DIN COIMBRA, PORTUGALIA.

La sfarsitul acestei etape a fost trimisa spre publicare intr-o revista cotata ISI si cu vizibilitate internationala o lucrare ce descrie o parte din rezultatele etapei I.

Rezumatul Etapei I este prezentat pe site-ul proiectului “ProWsper”: http://icechim-rezultate.ro/proiect.php?id=23, Contract 39/2017. Tot pe site-ul proiectului se regasesc si link-uri utile, descrierea proiectului, descrierea consortiului, obiective si rezultate estimate la nivel de consortiu international.  

Comunicari:

1. 13th International Conference on Materials Chemistry (MC13), 10–13 July 2017, Liverpool UK. Prezentare Poster P28: “Biocellulose Composite Hydrogels for Efficient Retention and Release of NPK Based Fertilizers”. Autori: Cursaru, Bogdan; Zaharia, Anamaria; Sirbu, Carmen; Sarbu, Andrei; Cioroianu, Traian; Radu, Anita; Laura; Florea, Ana Mihaela; Iordache, Tanta-Verona.

2. Bioinspired Materials 2017,  31 Aug.-1 Sept., Manchester Metropolitan University, Manchester, UK. Prezentare Poster P10: “Characterization of Bisphenol A-Imprinted Materials Obtained by Sol-Gel Technique”. Autori: Ana-Mihaela Florea, Tan?a-Verona Iordache, Anita-Laura Radu, Anamaria Zaharia, Steluta Apostol, Bogdan Cursaru, Hermine Stroescu, Mihai Anastasescu, Catherine Branger, Hugues Brisset, Vitalys Mba Ekomo, Andrei Sârbu.

3. Priorities of Chemistry for a Sustainable Development – PRIOCHEM 13, 25-27 Octombrie 2017, Biblioteca Centrala a Universitatii Politehnica Bucuresti, Bucuresti, Romania. Prezentare Orala O09: “New Poly(ethylene glycol) Composite Hydrogels with Nanozeolite as the Filler for Controlled Delivery Applications”; Autori: B. Cursaru, A. Zaharia, A.-L. Radu, A. Sarbu, T.-V. Iordache, A.-M. Florea, R. Ianchis, C.-M. Damian, T. Sandu, F.-X. Perrin, M. Teodorescu.

Meeting-uri si Work Shop-uri:

1.  WaterWorks2015 Projects Kick-off Meeting on the 6th April 2016, in Stockholm, Sweden (Folkets Hus Konferens - Stockholm City Conference Centre). Prezentare Orala a Proiectului ProWsper de catre Dr.ing. Tanta-Verona Iordache. Programul Meeting-ului si Prezentarea Proiectelor de catre fiecare Director de Proiect, poate fi accesat la adresa urmatoare: http://www.waterjpi.eu/index.php?option=com_content&view=article&id=571:ww2015-presentations&catid=80:documents&Itemid=1008

2. Work Shop: State-of-the-art in materials and methods for decontamination of soil and water, 10 Iulie 2017, INCDCP-ICECHIM, Bucuresti. In cadrul acestui WorkShop au fost prezentate 3 lucrari: “State of the art and emergent materials and methods for soil and water protection” Dr. Ing. Tanta-Verona Iordache; “Prezentarea Institutului si Activitatilor INCDPAPM- ICPA” Dr. Ing. Carmen Sirbu;  “Prezentarea Departamentului de Chimie si Activitatilor in cadrul Universitatii Coimbra” Prof. Dr. Artur Valente.

Lucrari in evaluare:

1. Bacterial cellulose-poly(acrylic acid-co-N,N’-methylene-bis-acrylamide) interpenetrated networks for the controlled release of fertilizers; Autori: Anamaria Zaharia, Anita-Laura Radu, Stela Iancu, Ana-Mihaela Florea, Iulian Minca, Victor Fruth-Oprisan, Mircea Teodorescu, Andrei Sarbu, Tanta-Verona Iordache. Trimis spre publicare in Polymers (IF=3.364; Special Issue), 2018. 

ETAPA II (FAZA UNICA)/ 2018

Titlu: Prepararea hibridelor de tip hidrogel-silicat pentru retentia/eliberarea de pesticide

Perioada: 01/01/2018 - 31/12/2018

Obiective propuse:

(I)Prepararea hibridelor de tip hidrogel-silicat modificat pentru retentia/eliberarea de pesticide

(II) Reproductibilitatea rezultatelor privind sinteza si caracterizarea hibridelor de tip hidrogel-silicat modificat pentru retentia/eliberarea de pesticide si nutrenti organici

(III) Comunicarea si diseminarea rezultatelor

Sumar:

Cercetarile efectuate in Etapa 2 a proiectului de INCDCP-ICECHIM Bucuresti s-au referit la experimentarile privind prepararea hibridelor de tip hidrogel-silicat modificat pentru  retentia/eliberarea de pesticide, precum si reproductibilitatea rezultatelor privind sinteza si caracterizarea hibridelor de tip hidrogel-silicat modificat, iar studiile experimentale ale celor de la ICPA s-au bazat pe caracterizarea dinamica a hibridelor hidrogel-silicat modificat urmarind kinetica si izoterma de adsorbtie-desorbtie in stare lichida a pesticidelor si nutrientilor organici.

Studiul de cercetare din aceasta etapa a avut ca si obiectiv principal modificarea microparticulelor de silicat mesoporos prin imprentarea moleculara gazda-oaspete a suprafetei polimerice vinilice cu molecule de templat in scopul crearii de cavitati selective pentru imobilizarea fizica ulterioara a pesticidelor in particulele de hidrogel-silicat modificat. De asemenea a fost studiat efectul sortului de silicat gazda asupra proprietatilor materialelor finale in vederea reproductibilitatii proceselor de sinteza si caracterizare. In acest scop au fost efectuate teste pe 2 tipuri diferite de zeoliti mesoporosi, un zeolit tratat termic si unul comercial, pentru a compara caracteristicile finale ale celor 2 silicati modificati.

In studiul re?inerii pesticidului dithane pe mostre de adsorbant tip MIP, in determinarea izotermelor de adsorb?ie, a fost evaluat? capacitatea de re?inere a compusul Dithane prin cuantificarea azotului din matricea acestuia.  Pe baza coeficien?ilor de corela?ie s-a estimat faptul c? echilibrul de re?inere a Dithane (pe baza parametrului determinat azot) a fost descris cu precizie comparabil? atât de modelul Langmuir cât ?i Freundlich, media coeficien?ilor de corela?ie pentru mostrele de MIP fiind de 0,9657 (Langmuir) ?i respectiv 0,9264 (Freundlich), totu?i procesul de re?inere în monostrat fiind avantajat. Valoarea ob?inuta pentru parametrul R_L (0 < R_L <1) indic? faptul c? procesul de adsorb?ie este favorabil. De altfel, s-a putut constata faptul ca probele de hidrogel cu MIP au inregistrat capacitati de adsorbtie mai mari decat cele de control de tip NIP.

Rezultate propuse si realizate:

In planul de Realizare al proiectului 39/2017, pe Etapa II/2017, au fost estimate urmatoarele rezultate:  participarea in cadrul unui WorkShop, 2 Comunicari stiintifice in cadrul Conferintelor Internationale si 1 lucrare redactata si trimisa spre publicare. Rezultatele obtinute au fost: 3 Comunicari Stiintifice, participarea in cadrul unui WorkShop, 2 lucrari ISI publicate si 1 lucrare Proceedings.

Tot in cadrul acestei etape au efectuate 3 deplasari in strainatate ce au avut ca scop diseminarea rezultatelor prin intemediul comunicarilor (doua comunicari tip poster si o prezentare orala) in cadrul conferintelor si activitati de networking (ce include si perspective de colaborare& noutati pentru proiect) prin intermediul unei vizite de lucru si a unui WorkShop organizat de catre Partenerul de Proiect Portughez, Universitatea din Coimbra. O deplasare in tara a fost efectuata in cadrul Conferintei Nationale BPC, organizata de catre Universitatea Politehnica din Bucuresti, pentru comunicarea rezultatelor cercetarilor sub forma unei comunicari orale.

Comunicari:

1. Anita-Laura Radu, Anamaria Zaharia, Ana-Mihaela Florea, Teodor SANDU, Bianca Georgescu, Bogdan Cursaru, Steluta Apostol, Andrei Sârbu, Carmen Sirbu and Tan?a-Verona Iordache, Biomimetic hybrid microparticles for retention/release of pesticides in order to minimize soil and water pollution, EUPOC 2018, COMO (ITALY), 20-24 May 2018, Comunicare Poster.

2. Sîrbu Carmen, Cioroianu Traian, St?nescu Ana-Maria, Nicoleta M?rin, Daniela Mihalache”Humic substances holdup on bio polymeric structures”,”8th International Multidisciplinary Scientific Conference on Earth & GeoSciences SGEM 2018”, ISSN 1314-2704, Comunicare Poster.

3. Tanta-Verona Iordache, Anamaria Zaharia, Anita-Laura Radu, Ana-Mihaela Florea, Carmen Sirbu, Steluta Apostol, Andrei Sarbu, Bio-based polymer adsorbents for the retention of organic nutrients and pesticides, Bucharest Polymer Conference 1^st ed, (BPC), 6-8 Iunie 2018, Prezentare Orala.

Vizita de lucru si Work Shop:

Workshop on How to protect water, soil, and plants production all together, Department of Chemistry, University of Coimbra, 7th May 2018, https://goo.gl/EC41ox

Dr. Ing. Tanta-Verona Iordache a prezentat lucrarea “Synthesis of bacterial cellulose hydrogels and clay particles for retaining organic nutrients and pesticides” iar Dr. Ing. Carmen Sirbu“Humic substances holdup on bio polymeric structures”.

 Lucrari publicate:

1. Anamaria Zaharia, Anita-Laura Radu, Stela Iancu, Ana-Mihaela Florea,Teodor Sandu, Iulian Minca, Victor Fruth-Oprisan, Mircea Teodorescu, Andrei Sarbu and Tanta-Verona Iordache, Bacterial cellulose-poly(acrylic acid-co-N,N0- methylene-bis-acrylamide) interpenetrated networks for the controlled release of fertilizers, RSC Adv., 2018, 8, 17635.  DOI: 10.1039/C8RA01733F

2. Elena Ionescu, Tanta-Verona Iordache, Carmen Elena Tebrencu, Ruxandra Mihaela Cretu,  Ana-Mihaela Florea, Anita-Laura Radu,  Anamaria Zaharia, Andrei Sarbu, Development of Single-step Protocols for the Separation of Naphtodianthrones from St. John s Wort Extracts, Rev.Chem, 2018, vol.69, 8, 2295-2299 http://www.revistadechimie.ro/archive.asp

3. Conference Proceedings, volumul 18, Water Resources, Forest, Marine and Ocean Ecosystems, Issue: 3.2 al conferin?ei ”8th International Multidisciplinary Scientific Conference on Earth & GeoSciences SGEM 2018”, pag.  227 – 233. https://sgemworld.at/sgemlib/spip.php?article11742&lang=en

FAZA 3: Prototiparea si evaluarea capacitatii prototipurilor de a sustine cresterea echilibrata a plantelor

BUGET FAZA:  354.390 RON

PERIOADA FAZA: 01.01.2019 - 31.12.2019

OBIECTIVELE SPECIFICE ALE FAZA 3

Activitate 3.1 - Prototiparea compozitelor pentru retentia/eliberarea de pesticide si nutrienti organici

Activitate 3.2 - Determinarea eficientei prototipurilor in spatii deschise

Activitate 3.3 - Comunicare si diseminarea rezultatelor

REZUMAT FAZA 3

Activitate 3.1 - Prototiparea compozitelor pentru retentia/eliberarea de pesticide si nutrienti organici

Primul obiectiv: Analizele structurale ale microparticulelor de argila modificate prin imprentatare moleculara au avut ca scop corelarea intre morfologie si proprietatile de adsorbtie. Din acest motiv hibridele imprentate si cele neimprentate au fost analizate in diferite etape de prelucrare, inainte de extractie si dupa extractie/conditionare in etapa finala de spalare. Rezultatele FTIR ale noilor hibride au indicat existenta benzilor caracteristice argilei si polimerului precum si cele atribuite pesticidului anorganic. Analiza DLS a dezvaluit ca procesul de modificare a microparticulelor de argila prin tehnica imprentarii moleculare gazda-oaspete a suprafetelor polimerilor vinilici a condus la o usoara crestere a dimensiunii particulelor, metoda utilizata neinfluentand intr-un mod semnificativ dimensiunea particulelor de argila, iar proprietatile investigate prin aceasta tehnica fiind reproductibile. Imaginile SEM ale pulberii de argila au prezentat existenta unei suprafete poroase, pori deschisi si inchisi. În cazul hibridelor pe baz? de argila (NIP si MIP dupa extractie) a fost observata o structura mai dens? ?i mai compact? dar indicand si formarea unor aglomerate de dimensiuni neuniforme datorita unor posibile schimbari de hidrofilicitate aduse de stratul polimeric.

Al doilea obiectiv: Noile stucturi hibride hidrogel-bioceluloz? (din etapa a doua) si hidrogel-argil? au fost sintetizate prin copolimerizare radical? initiat? de sistemul redox KPS/MS. Noile structuri compozite de hidrogel au fost caracterizate prin spectroscopia FTIR, prin analiza TGA/DTG, prin microscopie electronic? de baleiaj SEM, difractie de raze X si, de asemenea, caracterizat? prin gradul de umflare. Rezultatele au aratat ca gradul de gonflare la hidrogelurilor hibride sintetizate a fost influentat de incorporarea biocelulozei sau a argilei in structura hidrogelului (prezenta acestora a condus la formarea unor noi puncte de reticulare in structura hidrogelului, acest fenomen conducand la un grad de gonflare mai scazut).

Activitate 3.2 - Determinarea eficientei prototipurilor in spatii deschise

In proiectul ProWsper, ideea inovatoare a constat dintr-un material geotextil compozit, care contine în partea de jos un strat cu rol de drenare a excesului de ap?, în mijloc un hidrogel compozit pentru retinerea apei, îngr?s?mintelor, pesticidelor si nutrientilor din sol (în perioadele în care aceste substante sunt în exces) si pentru desorbtia catre la plante (atunci când au nevoie), iar in partea de sus a compozitului este un strat care permite transferul usor de mas? între hidrogel si r?d?cinile plantelor. De asemenea, cele dou? straturi împiedic? r?spândirea particulelor de hidrogel si, prin urmare, poluarea solului. Prototipurile astfel obtinute au fost testate de c?tre partenerul ICPA pentru a modifica în mod discret prototipurile (dac? este necesar), în functie de rezultatele obtinute în mediul simulat, si pentru a verifica parametrii optimi de retentie a compusilor tint? în conditii experimentale prin evaluarea sporilor de productie si evaluarea caracteristicilor produsului.

Activitate 3.3 In cadrul acestei activitati ICECHIM a redactat/trimis spre publicare 2 lucrari ISI, a trimis spre evaluare 2 cereri de brevet, a prezentat 2 lucrari sub forma de poster in cadrul a 2 Conferinte internationale si a participat in cadrul a 2 workshopuri cu 2 lucrari ce sumarizeaza rezultatele proiectului ProWper. ICPA a redactat/trimis spre publicare 1 lucrare proceedings, a participat la redactarea 1 cereri de brevet, a prezentat 1 lucrare sub forma de poster in cadrul unei Conferinte internationale.

DISEMINAREA REZULTATELOR

Cereri brevete nationale

1. Iordache Tanta Verona, Radu Anita Laura, Sârbu Andrei Zaharia Anamaria, Gavril? Ana Mihaela, Sandu Teodor, Apostol Steluta, Stoica Elena Bianca „Particule de polimeri imprentati molecular pe suport anorganic ?i procedeu de obtinere a acestora” Cerere OSIM A 00110/19.02.2019
2. Tanta Verona Iordache, Anita Laura Radu, Anamaria Zaharia, Andrei Sârbu, Carmen Sirbu, Ana Mihaela Gavril?, Teodor Sandu, Elena Bianca Stoica, Crina Thea Cojocaru, Razvan Edward Botez, Andreea Miron si Steluta Apostol „Compozit geotextil pentru protectia mediului si procedeu pentru obtinerea acestuia” Cerere OSIM A 00846/03.12.2019.

 Articole

1. Ana-Mihaela (Florea) Gavrila, Tanta-Verona Iordache, Teodor Sandu, Anamaria Zaharia, Anita-Laura Radu, Catherine Branger, Hugues Brisset, Elena-Bianca Stoica, Steluta Apostol, Andrei Sarbu, Molecularly Imprinted Polymer Pearls Obtained by Phase Inversion for the Selective Recognition of Hypericin, Materiale Plastice, 56(2), 2019, pp. 315-320.
2. Catalina Paula Spatarelu, Anita-Laura (Radu) Chiriac, Bogdan Cursaru, Tanta-Verona Iordache, Ana-Mihaela Gavrila, Crina-Thea Cojocaru, Razvan-Edward Botez, Bogdan Trica, Andrei Sarbu, Mircea Teodorescu, Vlad Tofan, François-Xavier Perrin, Anamaria Zaharia, Composite nanogels based on zeolite -poly(ethylene glycol) diacrylate for controlled drug delivery, Nanomaterials, MDPI, Trimis spre publicare
3. Sîrbu Carmen, Cioroianu Traian, Effects of fulvic acid on growth and productivity of tomato plants, SGEM International Scientific Conferences on Earth&Planetary sciences “Green Science for Happy Future”– Extended Sessions, Advances in Biotechnology, proceedings acceptat spre publicare.

Conferinte

1. Anamaria Zaharia, Anita-Laura Radu, Ana-Mihaela Gavrila, Teodor Sandu, Andreea Miron, Marilena Dumitru, Andrei Sarbu, Carmen Sirbu, Tanta-Verona Iordache, Hybrid microparticles for the retention/release of pesticides with application in agriculture, “World Congress on Functional Materials and Nanotechnology” (WCFMN 2019), 12-16 May 2019, Valencia, Spain.
2. A. Miron, A.-L. Radu, A. Zaharia, C.-T. Cojocaru, A.-M. Gavrila, T. Sandu, E.-B. Stoica, A. Sarbu, C. Sirbu, T.-V. Iordache, Zeolite microparticles modified by host-guest molecular imprinting for pesticides retention, „8th Graduate Student Symposium on Molecular Imprinting”, 28-30 August 2019, Berlin, Germany.
3. Sîrbu Carmen, Cioroianu Traian, Effects of fulvic acid on growth and productivity of tomato plants, SGEM International Scientific Conferences on Earth&Planetary sciences “Green Science for Happy Future”– Extended Sessions, 9-12 December 2019, Viena, Austria

Workshop-uri:

WaterWorks2015 Projects Midterm Evaluation Meeting and WATER JPI WorkShop for aliniation of on-going projects- Presentation of Midterm Report on ProWsper by Dr.ing. Tanta-Verona Iordache,26-29 May 2019, in Madrid, Spain.

1. WorkShop on project „ProWsper”-”Clay-Hydrogel Composites for the retention of organic nutrients and pesticides” presented by Dr. Ing. Tanta-Verona Iordache. 24-25 June 2019, Toulon, France.

FAZA 4: Demararea studiilor de demonstrare a eficientei prototipurilor in sere si stabilirea unor metode de reconditionare a umpluturii prototipurilor

BUGET FAZA:  126.433 RON

PERIOADA FAZA: 01.01.2020 - 31.03.2020

OBIECTIVELE SPECIFICE ALE FAZA 4

Activitate 4.1 – Stabilirea unor metode de reconditionare a umpluturii.

Activitate 4.2 – Demararea studiilor de stabilire a eficientei prototipurilor in sere.

Activitate 4.3 – Comunicarea si diseminarea rezultatelor.

REZUMAT FAZA 4

În aceast? etap?, experiment?rile s-au referit la demararea studiilor de demostrare a eficien?ei prototipurilor în sere ?i stabilirea unor metode de recondi?ionare a umpluturii prototipurilor. Astfel, în vederea îndeplinirii acestui scop principal, a fost avut în vedere ca ?i prim obiectiv al etapei stabilirea unor metode de recondi?ionare a umpluturii, urmat? de investigarea eficien?ei în sere intr-un prim ciclu de crestere al tomatelor. O parte dintre rezultatele ob?inute atât de catre entitatea coordonatoare (INCDCP- ICECHIM), cât ?i de c?tre partenerul ICPA, au fost materializate printr-o activitate de comunicare in cadul Workshopului organizat de catre ICECHIM la inceputul lunii Martie din 2020.

 Activitate 4.1 – Stabilirea unor metode de reconditionare a umpluturii

Primul obiectiv l-a constituit stabilirea unor metode de recondi?ionare a umpluturii la fa?a locului, cu scopul prelungirii duratei de via?? a produsului finit. Aceast? activitate a f?cut obiectul cercet?rilor INCDCP-ICECHIM.

In acest studiu, au fost reconditionate doua tipuri de hidrogeluri compozite, dup? cum urmeaz?: hidrogeluri hibride cu retea interpenetrata pe baz? de acid poliacrilic si celuloz? bacterian? (BC-PAA) pentru retentia acizilor humici si hidrogeluri hibride pe baz? de acid poliacrilic in care au fost incapsulate particule de perlit-organofilizat imprentat molecular cu mancozeb (PAA-pMIP) pentru retentia de pesticide. In toate cazurile, acidul poliacrilic (PAA), joac? rolul de material de baz? în procesul de ob?inere a hidrogelurilor, fie simple fie compozite (cu BC sau perlit). Pentru fiecare dintre cele doua tipuri de probe, au fost reconditionate si referintele corespunz?toare adica particule de PAA simple (fara celuloza bacteriana) si particule PAA-pNIP (organofilizate dar neimprentate cu mancozeb).

In ceea ce prive?te stabilirea unor metode de recondi?ionare a umpluturii, a fost adaptata o metoda utilizata si de catre partenerul ICPA pentru studiul de retentie/eliberare a pesticidelor ?i, respectiv, a nutrientilor, in cadrul etapelor precedente. Aceasta metoda presupune o spalare repetata a materialelor cu apa ultrapura. Confirmarea reconditionarii sau a purificarii matricilor polimere s-a realizat prin înregistrarea spectrelor FTIR inainte si dupa etapa finala de spalare a particulelor si prin inregistrarea spectrelor UV-vis a apelor de spalare dupa fiecare etapa de spalare. Spectrometria FTIR permite analiza structurii materialului in cele doua etapele, adica inainte si dupa spalare, in care se disting modificari asociate extractiei de nutrienti si pesticide, compusi retinuti in studiul pe coloane de levigare, in vreme ce, spectrele UV-Vis permit vizualizarea desorbtiei, in fiecare etapa de spalare, a compusilor din materialele studiate.

Activitate 4.2 – Demararea studiilor de stabilire a eficientei prototipurilor in sere

Al doilea obiectiv l-a constituit demararea studiilor de stabilire a eficien?ei prototipurilor în sere (dup? un ciclu de cre?tere a culturilor de tomate). In acest sens, pentru efectuarea studiilor de stabilire a eficientei prototipurilor de medii absorbante pe culturi in spatii protejate dupa primul ciclu de crestere a culturilor, activit??ile experimentale au urm?rit:

? Stabilirea plantei test ?i elaborarea schemei experimentale de re?inere în regim dinamic a substan?elor organice / produselor de protec?ie a plantelor;

? Înfin?area culturii cu planta test ?i desfa?urarea activit??ilor de între?inere;

? Analiza ?i interepretarea datelor experimentale;

? Realizarea de achizi?ii necesare desf??ur?rii activit??ilor prev?zute.

Activitate 4.3 – Comunicarea si diseminarea rezultatelor

In final, cel de-al treilea obiectiv al etapei l-a reprezentat valorificarea rezultatelor cercet?rii, prin participarea/organizarea de manifest?ri ?tiin?ifice de specialitate. In acest sens, coordonatorul ICECHIM a organizat un Workshop in cadrul caruia rezultatele obtinute au fost diseminate catre mediul stiintific si mediul economic. In cadrul acestui Workshop au participat, in calitate de invitati, toti Partenerii de Consortiu International (de la Univesitatea din Toulon si Universitatea de Coimbra) dar si invitati din mediul economic de la Institutul Norvegian de Bioeconomie (NIBIO, Oslo, Norvegia) si de la Intreprinderea Romana EDAS-EXIM. SRL (Bucuresti, Romania) ce dezvolta tehnologii de purificare a apelor si a apelor uzate. Totodata, un articol trimis spre publicare in revista MDPI Nanomaterials a fost acceptat si publicat on-line.

DISEMINAREA REZULTATELOR

            Valorificarea rezultatelor cercet?rii s-a realizat prin participarea/organizarea de manifest?ri ?tiin?ifice de specialitate. In aceasta etapa nu au fost realizate deplasari externe ale membrilor echipei de proiect. A fost realizata deplasarea dnei Carmen Sirbu la sediul Institutiei Coordonatoare pentru a participa cu o prezentare orala in cadrul Workshop-ului “Advanced Materials for Water and Soil Protection and Wastewater Purification” organizat de catre coordonatorul Proiectului, ICECHIM.

In cadrul acestui Workshop au participat cu comunicari orale toti Partenerii de Consortiu International (Prof. Xavier Perrin de la Univesitatea din Toulon si Prof. Artur Valente de la Universitatea de Coimbra) iar din cadrul Consortiului national ProWsper au fost prezentate urmatoarele lucrari orale :

1. Dr. Verona IORDACHE “Synthesis and characterization of new hydrogel-based composites with potential application in agriculture practices”

2. Dr. Carmen SIRBU “Evaluation of hydrogel-based composites for the retention of mancozeb pesticide and humic acids”

• Un articol trimis spre publicare anul trecut in revista MDPI Nanomaterials a fost acceptat si publicat on-line : Composite Nanogels Based on Zeolite-Poly(ethylene glycol) Diacrylate for Controlled Drug Delivery, 2020, Nanomaterials 10(2):195-215.

Summary 

The need for innovative strategies for water and soil protection that substitute the time-, energy- and resource-consuming remediation processes with other more efficient and environmentally-friendly is becoming urgent. In this respect, the interest of this project is to promote such solutions for public and private practitioners and to up-rise industrial competitiveness through economically sustainable technologies/products, in the Agriculture Field and indirectly in the Water Management aria. Therefore, this project practically develops protective composite layers (as end-products) with high efficiency towards pollution of underground water and soil, but without affecting the plants growth.

ProWsper is an experimental and demonstrative research project conducted in partnership with four prestigious Institutions, from three European countries (Romania, France and Portugal) that face these common problems. In order to succeed, the implementation gap from Prototyping to Marketing and thereafter to practitioners will be narrowed by social/industrial awareness campaigns using various channels.

Objective

Develop original, sustainable, and cost-effective solutions/products for protecting underground water and soil against nutrient and pesticide pollution while ensuring the well-balanced growth of plants (particularly, for greenhouses and small crop cultures). Applying such solutions/products during the fruit/vegetable growth cycles, reduces pollution and provides humid- and nutrient-stable environment for plant growth.

Results achieved so far and web-site

(i)                  4 ISI Peer-reviewed OA Papers published (1 in Revista de Chimie, 1 in Current Organic Chemistry and 2 in RSC Advances),  and 1 Proceedings Paper

(ii)                9 communications at international conference or symposia and 2 communications at national conferences,

(iii)               Organisation of 2 workshops together (knowledge exchange and awareness about the issues regarding water and soil pollution) with the kick-off and second work meeting (in Bucharest-Romania and Coimbra-Portugal, respectively),

(iv)              Construction of the ProWsper website dedicated to rising awareness of the project scope, objective and results (http://icechim-rezultate.ro/proiect.php?id=23&lang=en),

(v)                Concepts established for 3 materials types (hydrogels for inorganic/organic nutrients retention and clay-based materials for pesticide retention).

Work Performed and the Results achieved during the reporting period

 INCDCP-ICECHIM (P1)

The research carried out in this period by INCDCP-ICECHIM was related to the experiments concerning the preparation of hybrid particles for retention / release of pesticides and organic nutrients.

The first objective of ICECHIM was performing modifications on mesoporous zeolite and perlite (in parallel) by the host-guest molecular imprinting of Mancozeb using vinylic polymers in order to create cavities for the subsequent selective retention of pesticides in the matrix of the hydrogels.

For the selection of the plant protection product to be used in the experiments, a wide range of active compounds and commercially available substances have been analyzed. The main criteria for selecting the possible products to be tested was the mode of application and the ways of action, the cultures to which they can be applied, the type of pathogens on which they act, bearing in mind that the modified silicate particles will be introduced in a textile material and the device thus formed will be placed in the soil at an average depth of at least 15 cm. Of these, the Dithane M 45 product (with Mancozeb) was selected to perform the tests in steps I, II in 2017, 2018 with which the modified clay particles were imprinted.

The effect of the type of host clay (perlite or zeolite) on the properties of the final materials was also studied. Thus, in order to achieve the main objective of this experimental study, the following steps were taken: Obtaining new modified-clay by the host-guest procedure based on mesoporous zeolite or expanded perlite; Characterization of the inorganic matrix and the hybrids using the following techniques in order to obtain information on: the chemical composition (spectrum in Fourier transform infrared (FTIR), particle size and Zeta potential (dynamic light scattering (DLS) ), the chemical structure (X-ray diffraction (XRD)), microstructural analysis (scanning electron microscopy (SEM)), and textural properties (BET) for obtaining information on improving the adsorption capacity with the inorganic compound used as a reference. The synthesized materials can then be used as adsorbents for pesticide retention / release due to the textural properties of modified clay microparticles.

Using similar recipe for modified-clay by the host-guest procedure, without imprinting, perlite functionalized particles were obtained for the retention of organic nutrients. The synthesized materials were used as adsorbents for hummic acids retention / release but not as efficient. Therefore, the clay was substituted with biocellulose in the next step to ensure better compatibility with the organic nutrients.

The second objective of ICECHIM was to obtain composite hydrogels in granular form by reverse suspension polymerization for both pesticides and inorganic and organic nutrients. The principle of reverse suspension polymerization consists in dispersing the aqueous monomer and initiator solution in a water-immiscible organic solvent (cyclohexane, toluene, etc.), generally in the presence of an emulsifier or stabilizer. The polymerization reaction results in a polymer in the form of particles. In our experiments, we used paraffin oil for cosmetic use (cosmol, cosmol oil) as dispersion medium. Cosmol oil was used because because of its cosmetic use it is very pure and, therefore, contains no substances that affect the radical polymerization process of AA. The working method was inspired by two US patents describing the preparation of granular materials with increased water absorption capacity by polymerizing in reverse suspension of salts of acrylic acid dissolved in water using cyclohexane dispersion medium, and as sorbitan monolaurate emulsifiers / stabilizers and ethyl cellulose, respectively.

In a first approach, hydrogel particles for organic nutrient retention were synthesised. The results showed that the degree of swelling for the synthesized hybrid hydrogels was influenced by: (i) incorporation of bacterial cellulose (BC) into the polyacrylic acid structure (BC presenting new crosslinking points in the hydrogel structure, this phenomenon leading to a lower swelling degree); (ii) the concentration of bacterial cellulose (a higher concentration of BC led to a lower swelling degree); (iii) crosslinker concentration - (increase in MBA concentration resulted in a significant decrease in swelling). The hydrogel composites were for organic nutrients were compared to hydrogels obtained in bulk for inorganic nutrient. Further on, the targeted organic nutrients refer to hummic acids. Hence, the hybrid hydrogels were tested for adsorption/release on this particular organic nutrient (by Partner 2).

Using the similar procedure, reverse suspension polymerization, the modified-clay particles for pesticide retention were incorporated into the hydrogel matrix. Following this procedure, characterization of the hybrids using the following techniques in order to obtain information on: the chemical composition (spectrum in Fourier transform infrared (FTIR), particle size and Zeta potential (dynamic light scattering (DLS) ), the chemical structure (X-ray diffraction (XRD)), microstructural analysis (scanning electron microscopy (SEM)), and textural properties (BET) for obtaining information on improving the adsorption capacity with the inorganic compound used as a reference.

Concluding, the BC composite hydrogels for hummic acids retention/ release and perlite-composite hydrogels for Mancozeb retention/ release will be further used as fillers for the prototype protective layer preparation.

INCDCP-ICPA (P2)

In the first stage of 2017, following the documentation and studies conducted for the establishment of the main organic nutrient compounds to be used for the dynamic characterization of raw materials and hydrogel / biocellulose particles, humic substances were selected to be the most representative in this sense. To determine the dynamic retention capacity of the organic substances by the hydrogel / biocellulose particles, the following steps were taken:

ü  obtaining and characterization of organic compounds used experimentally

ü  development and validation of a rapid analysis method for organic compounds;

ü  elaboration of the experimental scheme for the dynamic retention of organic substances;

ü  analysis of solutions of organic substances collected in the experimental variants;

ü  processing of experimental data

In the first stage of 2017, the following actions were carried out in the setting of target pesticides and types of crops and soils for the use of the composites as well as the dynamic characterization of the raw materials and modified silicate particles:

ü  from a range of plant protection products, the product DITHANE M 45 has been selected with the active substance  named mancozeb, a substance found in other commercial products that are on the market

ü  elaboration of the experimental scheme for dynamically retaining of the mancozeb compound on the material named MIP EXTRAS;

ü  carrying out  the dynamic retention experiment of mancozeb;

ü  carrying out the total nitrogen analyzes of the solutions collected in the experimental variants;

ü  processing of experimental data

In 2018 studies were conducted on the retention of Dithane on MIP (determination of adsorption isotherms). The ability to retain the DITHANE compound by determining the nitrogen in the matrix was assessed. The equations used were Langmuire and Freundlich. Based on the correlation coefficients, it is estimated that DITHANE retaining equilibrium (based on the nitrogen parameter) was described with precision comparable to both the Langmuire and Freundlich models, with the average correlation coefficients for the six samples 0.9771 (Langmuire) and 0.9163 (Freundlich) respectively, however, the retention process in the monolayer is advantageous. The value obtained for the RL parameter (0

In 2018, the study of the retention of organic substances (humic acids) was carried out - determination of adsorption isotherms. The equilibrium adsorption data of humic substances were modeled using the Langmuir and Freundlich isotherm models, and the matching measure was evaluated by the value of the correlation coefficients (R²). The equations used for the determination of retention isotherms for humic substances (AH) on the adsorbent were Langmuire and Freundlich.

On the basis of the correlation coefficients the balance of holding the humic substances was estimated with comparable accuracy using Langmuire and Freundlich model, the average correlation coefficient for the six samples are 0.9285 (Langmuire) and 0.9163 ( Freundlich). The value obtained for the RL parameter (0

University of Toulon (P3)

The first task performed in by MAPIEM was to determine the conditions for the preparation of acrylic hydrogel matrixes with the optimal properties in terms of swelling degree (SD) water retention under thermal or mechanical stress (WR), loading capacity and slow release properties. We also systematically measured the reswelling capability of the hydrogels as it is an important property in the field of agriculture. The nutrient selected for this study was a nitrogen fertilizer (urea). Two different strategies were tested: an ex-situ loading method (the two-step NIP method) and an in-situ loading method (the one-step MIP method). Polyacrylate hydrogel was prepared by radical polymerization of acrylic acid (and acrylamide co-monomer) using ammonium persulfate and N,N’-methylenebisacrylamide as initiator and crosslinking agent, respectively. The main purpose of this study was to study the impact of building acrylic hydrogels in presence of nitrogen fertilizer on its structure and swelling/release properties (the so-called in-situ loading method). In this respect the following were systematically investigated:

• the effect of the neutralization degree of acrylic acid, the crosslinker content and acrylamide content
• the influence of the reswelling time on the saturated absorbency is more significant for the hydrogels prepared by the ex-situ method. Moreover, the saturated absorbency of the MIP hydrogels is less dependent on the crosslinker content than the NIP hydrogels.
• the water retention capacity of hydrogels is also an important parameter because it helps to mitigate the adverse effects of drought periods on the growth of the plant. These water retention properties were studied by subjecting the saturated hydrogels to a centrifugal force or placing them in an oven at a temperature of 60 °C. The effect of CL content on the water retention capacity of MIP and NIP hydrogels clearly show that MIP hydrogels have a high capacity to retain water under the effect of a pressure or temperature.
• the mechanical strength of the hydrogels was tested by performing tensile tests on standard size hydrogel specimens.
• the crosslinker content and the method used to prepare the hydrogel were found to have an impact on mechanical properties.
• the release rate of urea was also systematically investigated. A slower release of urea was observed for the hydrogel prepared by the MIP method. After a first urea release, the MIP hydrogel was reloaded with urea. The second release curve obtained for this MIP sample is similar to the release curve of the NIP sample. Consequently, there is no memory of the urea print for the acrylic network which means that the hydrogel prepared by the in-situ loading method cannot be definitely considered a molecular imprinting polymer. This is not surprising considering the extensive deformation of hydrogels during water sorption.

The most important observations are:

1- The hydrogels prepared by the in-situ loading method showed much better water retention capacities both under mechanical stress and thermal stress compared to the hydrogels prepared by the ex-situ loading method.

2- The rate of urea release is generally lower when the hydrogels are prepared by the in situ loading method. However, the advantage of the in-situ loading method is lost after subsequent release-reloading cycles.

3- This study allowed defining the best conditions to obtain hydrogel with optimized swelling, water retention and urea release properties

MAPIEM are currently using these conditions to prepare acrylic-kaolin hybrid hydrogels. Two different strategies for the incorporation of kaolin are investigated. The results are partial at the moment and should be finalized by the end of February 2019.

University of Coimbra (P4)

Partner P4 (UC) has carried out the physico-chemical study of phytopharmaceutics in terms of their kinetics in aqueous solution. Four different phytopharmaceutical have been chosen: Glufosinate-amonium (GlA), Cymoxanil, Imidacloprid, and zinc and manganese N-[2-(sulfidocarbothioylamino) ethyl]carbamodithioate. These active substances are used in the formulations of the following pesticides: Basta, Milraz, Confidor O-TEQ and Mancozan, respectively. These phytopharmaceuticals have been chosen taking into account their particular efficiency toward tomato cultures, as it was decided by the consortium.

The measurement of the interdiffusion coefficients of those compounds in aqueous solutions was carried out; the effect of Glufosinate-ammonium in ammonium nitrate-salt containing solutions has also been measured by using the Taylor dispersion technique. Additionally MD calculations have employed the GROMACS program and the AMBER force field with GAFF parameters. The standard procedure for AMBER force field has been employed to build the topology of pesticides: (i) the OpenBabel program has been employed to generate the 3D molecular structures; (ii) then the 3D geometry is optimized and the partial charges were calculated at the HF/6-31G^* level of theory by using the GAMESS package and the RESP fitting protocol, as implemented in the RED program; (iii) the AnteChamber PYthon Parser interfacE (ACPYPE) tool was applied to generate the geometry and topology input files for GROMACS. The preparation of the system to be studied is completed by putting the molecules, in the simulation cubic-box and, then, it is solvated with water molecules that are described with the TIP3P model. In the cases of charged pesticides, we also added counter ions (i.e., Na+ or Cl−) to the simulation box so that the whole system becomes neutral. After energy minimization of the simulating system, equilibration was performed during 1 ns within the NVT and NPT ensemble, where the temperature and pressure have been fixed at 300 K and 1 bar. Once the system is equilibrated, the production MD run is carried out for a longer simulation time, 50 ns. We have employed the same simulation conditions as for equilibration step. The MSD chart and the value of D were calculated with the msd tool from GROMACS which employs the usual Einstein expression.

From these measurements, it was possible to obtain useful information (e.g., thermodynamic, transport and structural parameters) and, consequently, to reach a better understanding of the structure of these aqueous systems, supplying the scientific and technological communities with data on these important parameters in solution transport processes. From all the pesticides tested it can be concluded that Glufosinate ammonium offers less frictional resistance to motion through solutions, whilst in the opposite side Mancozeb has the lowest diffusion. The analysis of data shows that the salt has a salting-in effect on the Glufosinate-ammonium.

P4 has also carried out MD simulations to investigate the ability of several polymers to remove four pesticides from water. MD calculations have employed the GROMACS program and the AMBER force field with GAFF parameters. The study has shown that MD simulations are a powerful methodology for the screening of polymers and environmental conditions that are potentially effective for cleaning water and soils contaminated with pesticides. The main results from the present work show that chitosan is the polymer that establishes the strongest interactions with the pesticides. Such interactions are mainly due to the formation of hydrogen bonds. In turn, protonated polyacrylic acid can also establish hydrogen bonds with cymoxanil, glufosinate-amonium and imidacloprid, but it is not effective for Mancozeb. In addition, deprotonated polyacrylic acid is totally non-effective in establishing interactions with all pesticides.

Based on these studies chitosan-based hydrogels have been developed by partner P4. The sorption of cymoxanil (CYM) on those hydrogels leads to some erosion-like of hydrogel surface; the sorption follows a Freundlich and BET sorption for gels without and with cyclodextrins, and the latter show a high adsorption efficiency [MSc. Thesis of Gianluca Utzeri].

Following a similar procedure than that described previously, MDS have been used for the study of permeation of pesticides in membranes; thus, the effect of different pesticides in polypropylene (PP) has been carried out.

Conclusions:

- To the best of our knowledge, for the very first time, diffusion coefficients for a series of pesticides have been measured.

- Chitosan-based hydrogels show excellent properties for retention of Cymoxanil.

- Polypropylene shows excellent interaction properties with different pesticides, as seen by MDS, showing to be a good candidate for the preparation of geotextile membranes. 

Table of Deliverables 

Consortium Meetings

List of Publications produced by the Project - Open Access