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Arifin Sandhi ARSENIC REMOVAL BY PHYTOFILTRATION AND SILICON TREATMENT A POTENTIAL SOLUTION FOR LOWERING ARSENIC CONCENTRATIONS IN FOOD CROPS Arifin Sandhi April 2017 TRITA-LWR PHD-2017:02 ISSN 1650-8602 ISBN 978-91-7729-332-3 Arifin Sandhi TRITA-LWR PHD-2017:02 © Arifin Sandhi 2017 Doctoral Thesis in Land and Water Resources Engineering Department of Sustainable Development, Environmental Science & Engineering KTH Royal Institute of Technology SE-100 44 STOCKHOLM, Sweden Reference to this publication should be written as: Sandhi, A (2017) “Arsenic removal by phytofiltration and silicon treatment-A potential solution for lowering arsenic concentrations in food crops” TRITA-LWR PHD-2017:02 ii Arsenic phytofiltration and silicon application-lowering arsenic concentrations in food crops Dedicated to My Parents & the millions of people affected by arsenic contamination around the globe iii Arifin Sandhi TRITA-LWR PHD-2017:02 iv Arsenic phytofiltration and silicon application-lowering arsenic concentrations in food crops SUMMARY IN SWEDISH Halvmetallen arsenik (As) tillhör ett av de grundämnen som blivit ett globalt hälsohot. Mer än 100 miljoner människor runt om i världen har redan direkt eller indirekt påverkats av denna metall som en förorening. Befolkningen i många utvecklingsländer får sitt dricksvatten från lokala brunnar med arsenikhaltigt vatten och där reningsmetoder saknas. Förutom till dricksvatten, används grundvatten till jordbruket och om det är förorenat med arsenik kan det tas upp i livsmedelsgrödor. Vid odling av ris är risfälten ofta vattendränkta för att skapa förutsättning för tillväxt och omfattande användning av grundvatten påverkar upptaget av arsenik i riskorn. Ett antal förorenade områden finns särskilt i södra Asien, där innehållet av arsenik i ris lokalt är relativt högre än ris från andra delar av världen. Jämfört med maximalt tillåtet innehåll i dricksvatten (10 mikrogram/L eller 10 ppb), så finns inte regler för tillåtet innehåll i livsmedel i flertalet utvecklingsländer. I avhandlingen undersöktes innehållet av arsenik i hybridiserade sorter av ris och i lokala rissorter (Oryza sativa) för att bestämma variationen beroende på vilka jordbruksmetoder (t.ex. bevattningskrav) som använts. Resultaten visade för såväl riskorn som skal att det beror på den s.k. ackumuleringsfaktorn (AF). Detta AF värde verkade påverkas av den specifika odlingsjorden och koncentration av arsenik i denna samt de olika rissorterna. Genom screening av rissorternas AF värde kan man få en effektiv strategi för att minska upptaget av arsenik i livsmedelskedjan. Följaktligen bör också innehållet av arsenik i bladgrönsaker uppmärksammas särskilt då de konsumeras som råa grönsaker (t.ex. sallad). Användningen av kisel (Si), ett av de mest förekommande grundämnena i jordskorpan och med en kemi som liknar arsenikens, har befunnits kunna minska upptaget i spannmålsgrödor t exvete. I avhandlingen undersöktes hur koncentrationen av arsenik i sallad (Lactuca sativa) påverkades av tillförsel av kisel och det konstaterades att det kunde minska koncentrationen i den ätliga delen av salladen. Slutsatsen var att kisel kan tillföras jorden för att arsenikupptaget ska minska till grödor och grönsaker, särskilt i förorenade områden. Det är känt att vissa växter har särskilt stor förmåga att ta upp arsenik och ansamla det i vävnaden. Denna egenskap kan utnyttjas vid en saneringsmetod av arsenikförorenad mark eller vatten som kallas fytoremediering. Jämfört med mekanisk och kemisk sanering, har växtbaserade saneringstekniker blivit uppmärksammade på grund av att de är ekonomiska och har fördelar ur hållbarhetsperspektiv. Bland de växtarter som inte undersökts så mycket är fytoremediering mha undervattensväxter s.k. fytofiltrering. En akvatisk mossart (Warnstorfia fluitans) som växer i gruvområden i norra delen av Sverige, där hög koncentration av arsenik konstaterades i vattensystemen, studerades med avseende på fytofiltrering. I avhandlingen undersöktes därför om denna vattenmossa har förmåga att binda arsenik som är löst i vatten och v Arifin Sandhi TRITA-LWR PHD-2017:02 om dess upptag från vattnet kan bidra till att minska innehållet av arsenik i livsmedelsgrödor. Vattenmossan (W. fluitans) odlades i vatten med låg koncentration av arsenik (74 µg As/L) och försöket visade ett snabbt avlägsnande (upp till 82%) inom kort tid. Mossan befanns fast fixera oorganiska arsenikformer (arsenat och arsenit) i sin växtvävnad. Slutsatsen av försöket var att denna vattenmossa har hög potential för fytofiltrering av arsenik i synnerhet i tempererade områden. När det gäller effekter av vattnets pH, temperatur och syresättning på mossans arsenikupptag så visade det sig att låga pH-nivåer (pH 2,5) orsakade stress hos mossan och lägre upptag oavsett oorganisk form av arsenik. Förmågan att hålla kvar arsenik i vävnaden testades vid både låga (12°C) och höga (30°C) vattentemperaturer. Inga tecken syntes på att arsenik skulle frisläppas utom när vattnet innehöll arsenat efter behandlingstiden 96 timmar. Lågt syreinnehåll i vattnet visade sig påverka arsenik upptaget positivt jämfört med hög syresättning. Möjligheten att använda den studerade vattenmossan som fytofilter i en anlagd våtmark för att rena vattnet innan det används för salladsodling, visade att metoden avsevärt skulle minska innehållet av arsenik i ätbara delar. Slutsatsen är att lämpliga strategier att minska koncentrationen av arsenik i livsmedel t ex ris, är att tillämpa screening av AF-värdet på grödor i hot-spot områden eller att tillföra kisel under odlingen. Förutom dessa verkar den studerade vattenmossan ha potential att ackumulera arsenik från förorenat vatten, åtminstone i tempererade klimatområden, och därmed bidra till en hållbar och miljövänlig lösning för att minska innehållet i grödor vid bevattning. vi Arsenic phytofiltration and silicon application-lowering arsenic concentrations in food crops ACKNOWLEDGMENT First, I would like to warmly acknowledge my supervisor at Stockholm University, Maria Greger, who has always been full of creativeness, motivation and support. The research question that I focused on in my PhD thesis was very unique and we could not find any external agency funding in the beginning, despite intense efforts. Maria realised the magnitude and significance of this problem and in discussions she encouraged me to take on the challenge. I been working with her since my Master’s studies at Stockholm University in 2009 and she is really a great group leader and the best supervisor any student could ask for. I was fortunate to have such a mentor in the initial period of my research career. I strongly believe the passion for research in my mind was greatly nourished by her continuous support and encouragement. I wish to be a similar example to my future students, providing the same level of inspiration, motivation and kindness that she gave to me. I also want to thank my principal supervisor at KTH, Gunno Renman, for providing real-time support at a very crucial time in my PhD studies, without you it would have been almost an impossible task to move forward. Gunnar Jacks, for providing practical help during the initial period of my PhD studies at KTH and also during the reviewing process for the rice manuscript. Tommy Landberg, I deeply acknowledge your support since my postgraduate studies started in Sweden. Your kind smile and help in the learning process in the laboratory made me confident in different kinds of critical analysis, especially arsenic speciation in plant samples. I am sure that in my future career, I will always miss your smile in the laboratory. My former colleague from the Plant Metal Research Group at Stockholm University, Claes Bergqvist, I owe you great thanks. You have given me so much practical information about arsenic analysis. Besides the laboratory, you were one of the best office roomies in my whole life. I will miss your cheerful talk in lunch hours. Tariq Javed, thanks a lot for your kind support during your time in the Plant Metal group. Sylvia Lindberg, I will never forget your caring smile during my whole study period. Special thanks to Hsinyu Wang for your outstanding work and help during one of my experiments. You did great work during your exchange study time in our group. A number of guest researchers worked in our Plant Metal group during my PhD studies, I am really thankful to Kader vai, Kabir vai, Marek, Basir, Jieyuan, Maria for your nice company. Staffan Mellvig, thank you very much for your time and helpful advice. You inspired me a lot to go to the gym after work! Eva Roubeau, your exchange time in our Plant Metal group was so memorable and joyful, many thanks from me. Nicoleta and Lillvor, thanks a lot for your help in the laboratory. Thanks to Olle Wahlberg, Dept. of Chemical Engineering, KTH, for giving me the chance to take part in the water chemistry course, which I enjoyed very much. I also acknowledge my co-authors in my scientific articles: Meththika Vithanage, Beata Dabrowska, Arun Mukherjee and Prosun Bhattacharya. vii Arifin Sandhi TRITA-LWR PHD-2017:02 Head of the department Ove Eriksson, former head Peter Hambäck and head of Plant Physiology Division Lisbeth Jonsson from the Dept. of Ecology, Environment and Plant Sciences (DEEP), Stockholm University, are greatly acknowledged for giving me their permission to continue my research work and to use the facilities at SU. The faculties at DEEP, Stockholm University, especially Ulla, Jonas, Clare, Mats, Barbro, Ellen, Sara, Lotta, Lina, and PhD student Konrad, Pil, Thomas, Van, Chen, Olle and Marco, all of you are greatly acknowledged for your support and good company during my time in DEEP. Thanks also to DEEP staff who provided administrative and logistics support during my studies, especially Siw, Åsa, Erica, Johan, Lars, Erik, Susanne, Anna, Ingela, Ahmed and Peter. Special thanks to my work colleagues and friends Tobias Robinson, Clara Neuschütz and Daniel Nordstrand for making my study period a good time. To my former and present colleagues from Land and Water Resources Engineering Division, KTH, Jon Petter, Helfrid, Ashis, Carin, Alireza, Agnieszka, Lily, Zou, Rajabu, Ezekiel, Lea and so many others! Thanks a lot – I had a really good time there.
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