Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences Arsenic Occurrence and Arsenic Occurrence and Innovative Technologies Innovative Technologies Development for Arsenic Development for Arsenic Pollution control in China Pollution control in China Qu Jiuhui*, Liu Ruiping, Zhang Gaosheng Qu Jiuhui*, Liu Ruiping, Zhang Gaosheng State Key Laboratory of Environmental Aquatic Chemistry State Key Laboratory of Environmental Aquatic Chemistry Research Center for Eco-Environmental Sciences Research Center for Eco-Environmental Sciences Chinese Academy of Sciences Chinese Academy of Sciences
OUTLINE � Arsenic and arsenism occurrence in China � Approaches and strategies for arsenic pollution control � What we are doing for arsenic pollution control � Strategies for arsenic pollution control in China � Innovative technologies development in China � Small systems for arsenic removal in distributed rural areas � Innovative Processes available in Municipal drinking water plant � Conclusions
Arsenic occurrence via drinking water in China Population exposing to high arsenic (>50 ppb): >5 million, mainly in rural areas More people are included as As exposure due to more strict standard for As in drinking water (<10 ppb) As pollution distribution: 11 provinces/Autonomous Regions/Municipalities Arsenism rate in high-As areas: 15.54%
Arsenic pollution distribution 6 th 1 st Inner Xinjiang 5 th Jilin Mongolia 2 nd Shanxi 3 rd Qinghai 4 th Anhui Taiwan Referenced Ranking between provinces /Autonomous Regions /Municipalities
Concentration (ppb) 100 120 140 160 180 Arsenic pollution cases: Beijing Dongzhuang 20 40 60 80 0 Sishang Baixingzhuang Yuanwangzhuang Matouzhuang Among these 14 villages, 12 villages exceed 10 μ g/L and 2 exceed 50 Houshayu Jixiangzhuang Arsenite Arsenate Gucheng Kuliushu Xitiangezhuang Huimingying Qianshayu Tiejiangying suburb Huoshengying μ g/L Enterprise
2 nd cases: Shanyin, Shanxi province County well Household well Skin keratinization Photos Taken on 25 th , Jan, 2007 As pollution occurs in 42 villages Population being exposed to arsenic: 35,000 Simultaneous presence of arsenic and fluoride
Arsenic pollution occurrences in typical provinces As Media and Province areas concentrati Affected Arsenism underground s (km 2 ) on population cases situations ( µ g/L) Underground 3,000 ~850 100,000 2,000 Xinjiang >100m Underground Inner 1,500 ~1860 1 million 3,000 10~50m Mongolia Underground 1,500 ~1930 1 million 4,000 Shanxi 10~70m 67 Underground ~207 60,000 670 Jilin villages 22 Underground ~2,000 25,000 500 Ningxia villages Underground 4 villages ~318 12,200 260 Qinghai Underground 5 villages ~150 86,900 8 Anhui Underground 5 villages ~143 60,300 0 Beijing Underground Taiwan 4 villages ~1,800 N.A. N.A. 100~280m district N.A.: not Referenced available
OUTLINE � Arsenic and arsenism occurrence in China � Approaches and strategies for arsenic pollution control � What we are doing for arsenic pollution control � Strategies for arsenic pollution control in China � Innovative technologies development in China � Small systems for arsenic removal in distributed rural areas � Innovative Processes available in Municipal drinking water plant � Conclusions
What are doing in China… Aiming to supply safe drinking water to people in rural areas, including arsenic control … Endeavors from the governm ent predominant, constructive and effective Non-Governm ental Organization ( NGO) Efforts we are groping and striving … Com m ercial investm ent and m arketization rare, but being stimulated and advocated
Efforts from government 2000~2005, 11.7 billion RMB from central government, 67 million people being benefited 2005~2006, 2 billion RMB from central government, 11 million people being benefited 2007~2012, 32 billion RMB from central government, 27.9 billion RMB from local government, 6.5 billion RMB from local residents, aiming to providing safe drinking water to 160 million people � The perennial cost should be evaluated for residents � The operation, maintenance and fittings replacement should be well supervised for
NGO efforts Chinese Academ y of Sciences ( CAS) : Technical expertise China Foundation for Disabled Global Health and Persons ( CFDP) : Project Education Foundation: Funding provision execution and management
NGO efforts � The 1 st water station installation was finished on Sep. 27th, 2007 in Shanyin County; � The another 5 stations are expected to be finished in 2008; � In the future, more stations … The operational models are very important for the sustainable development of NGO efforts
Strategies for arsenic pollution control Changing source w ater � Being restricted, if absence of satisfactory and safe water source � Great engineering investment for water transportation systems � Water quality should be well evaluated except for arsenic Treatm ent facilities installation ( recom m ended) � Without great pipeline constructions and corresponsive investment � Less expense required, more people benefited at the same � The development of technologies and systems for arsenic investment removal from drinking water is of critical importance in � Being available and effective, even without satisfactory China source water � Easy to handle, cost effective, being available in rural � Safe water quality assurance if being well managed
OUTLINE � Arsenic and arsenism occurrence in China � Approaches and strategies for arsenic pollution control � What we are doing for arsenic pollution control � Strategies for arsenic pollution control in China � Innovative technologies development in China � Small systems for arsenic removal in distributed rural areas � Innovative Processes available in Municipal drinking water plant � Conclusions
USEPA, 2003
Researches in RCEES, CAS Novel Adsorbent s High As(III) Low cost performance removal
Ferric and manganese binary oxides (FMBO) Preparation Fe 2+ stock solution Base solution Permanganate stock solution Suspension of Ferric and manganese binary oxides (FMBO) aging aging filtration filtration drying Power FMBO
FMBO Characterization Element Wt% At% 24.02 24.32 MnK 75.98 75.68 FeK SEM/EDX analysis Fe:Mn ≈ 3:1 Oxidation and adsorption abilities
Maximal Adsorption Capability Maximal adsorption potential adsorbents references As(III) (mmol As(V) (mmol g -1 ) g -1 ) FMBO 1.77 (pH4.8) 0.93 (pH4.8) This study Manganese dioxide 0.13 0.1 Lenoble et al. Geothite / 0.53 (pH3-3.3) Matis et al. Al 2 O 3 /Fe(OH) 3 0.12 (pH 6.6) 0.49 (pH7.2) Hlavay and Polyak Fe(III)-loaded sponge 0.24 (pH 9.0) 1.83 (pH 4.5) Munoz et al. Fe-Mn-mineral 0.16 (pH 5.5) 0.09 (pH 5.5) Deschamps et al. TiO 2 0.43 (pH 7.0) 0.55 (pH 7.0) Bang et al. Zhang GS, Qu JH, et al., Water Res., 2007, 41: 1921-1928
Proposed Mechanisms for As(III) Removal 1 st Step: As(III) adsorption onto FMBO ≡ M − OH surfaces As(III)(aq) + (–S Fe-Mn ) → As(III) –S Fe-Mn (1) As(III)(aq) + (–S Fe-Mn ) → As(III) –S Fe-Mn (1) ≡ M − OH 2 nd step: As(III) oxidation with manganese As(III) ≡ M − OH oxides 2MnO 2 + H 3 AsO 3 + H 2 O → 2MnOOH* + H 2 AsO 4- + H + (2) 2MnO 2 + H 3 AsO 3 + H 2 O → 2MnOOH* + H 2 AsO 4- + H + (2) ≡ M − OH 2MnOOH*+ H 3 AsO 3 + 3H + → 2Mn 2+ + H 2 AsO 4- +2 H 2 O (3) 2MnOOH*+ H 3 AsO 3 + 3H + → 2Mn 2+ + H 2 AsO 4- +2 H 2 O (3) ≡ M − OH Arsenic species transformation and ≡ M − OH Manganese dioxides reductive ≡ M − OH dissolution As(V) + Mn 2+ 3 rd step: As(V) adsorbing onto ferric oxides ≡ M − OH ≡ M − OH sites As(III) –S Fe-Mn + As(V)(aq) → As(V) –S Fe-Mn +As(III)(aq) (4) As(III) –S Fe-Mn + As(V)(aq) → As(V) –S Fe-Mn +As(III)(aq) (4) B O F M r f a c e s s u The reductive dissolution of manganese oxides changes the surface characteristics of adsorbents, promotes the formation of active sites available for arsenic adsorption, and facilitates arsenic removal. Zhang GS, Qu JH, et al., Environ. Sci. Technol, 2007, 41: 4613 4619
But engineering application? How to develop innovative technologies, based on FMBO, available for small systems and large scale drinking water plants?
1 st : Innovative Processes for small systems Porous Porous Porous carrier carrier carrier Active s Active s Active s pecies pecies pecies (FMBO) (FMBO) (FMBO) in s in s in s itu coating itu coating itu coating in s in s itu embedded itu embedded regeneration regeneration ars ars ars enic ads enic ads enic ads orption orption orption ars ars ars enic ads enic ads enic ads orption orption orption In Situ Coating and Embedded Regeneration
In Situ Coating and Embedded Regeneration Porous out out in in carrier KMnO 4 FeSO +NaOH Feasible in engineering, 4 Repeated several easy to be auto- times controlled
Coated on porous materials Coated on Coated on diatomite zeolite
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