Iron arsenic desorption

Oxidation of arsenic-bearing pyrite with adsorption onto iron oxides and/or other metal (oxy)(hydr)oxides Nitrate reduction by pyrite oxidation (note that Appelo and Postma, 1999 referred to pure rather than arsenian pyrite) Manganese oxide reduction and release of sorbed arsenic Fe(lll) reduction on oxide surfaces changes net charge leading to arsenic desorption Iron oxide reductive dissolution and release of sorbed arsenic catalyzed by NOM degradation... 

Arsenic desorption upon anaerobiosis has been ascribed to both the reduction of arsenic, from arsenate to arsenite, and iron(III), the latter leading to tire... 

The mobility of arsenic compounds in soils is affected by sorp-tion/desorption on/from soil components or co-precipitation with metal ions. The importance of oxides (mainly Fe-oxides) in controlling the mobility and concentration of arsenic in natural environments has been studied for a long time (Livesey and Huang 1981 Frankenberger 2002 and references there in Smedley and Kinniburgh 2002). Because the elements which correlate best with arsenic in soils and sediments are iron, aluminum and manganese, the use of Fe salts (as well as Al and Mn salts) is a common practice in water treatment for the removal of arsenic. The coprecipitation of arsenic with ferric or aluminum hydroxide has been a practical and effective technique to remove this toxic element from polluted waters... 

Whereas studies have been carried out on the factors (surface coverage, residence time, pH) which influence the desorption of arsenate previously sorbed onto oxides, phyllosilicates and soils (O Reilly et al. 2001 Liu et al. 2001 Arai and Sparks 2002 Violante and Pigna 2002 Pigna et al. 2006), scant information are available on the possible desorption of arsenate coprecipitated with iron or aluminum. In natural environments arsenic may form precipitates or coprecipitates with Al, Fe, Mn and Ca. Coprecipitation of arsenic with iron and aluminum are practical and effective treatment processes for removing arsenic from drinking waters and might be as important as sorption to preformed solids. 

Lafferty BJ, Loeppert RH (2005) Methyl arsenic adsorption and desorption be-hatior on iron oxides. Environ Sci Technol 39 2120—2127 Le XC (2002) Arsenic speciation in the environment and humans. In Frankenberger WT Jr (ed) Environmental chemistry of arsenic. Marcel Dekker, Inc. New York, pp 95-116... 

Liu F, De Cristofaro A, Violante A (2001) Effect of pH phosphate and oxalate on the adsorption/desorption of arsenate on/from goethite. Soil Sci 166 197-208 Livesey NT, Huang PM (1981) Adsorption of arsenate by soils and its relation to selected properties and anions. Soil Sci 131 88-94 Manceau A (1995) The mechanism of anion adsorption on iron oxides Evidence for the bonding of arsenate tetrahedra on free Fe(0, OH)6 edges. Geochim Cosmochim Acta 59 3647-3653. 

Dissolved arsenic is correlated with ammonia (Fig. 4), consistent with a release mechanism associated with the oxidation of organic carbon. Other chemical data not shown here provide clear evidence of iron, manganese and sulfate reduction and abundant methane in some samples indicates that methanogenesis is also occurring. It is not clear however if arsenic is released primarily by a desorption process associated with reduction of sorbed arsenic or by release after the reductive dissolution of the iron oxide sorbent. Phreeqc analysis shows PC02 between 10"12 and 10"° bars and that high arsenic waters are supersaturated with both siderite and vivianite. 

A precipitation of the iron hydroxides is also observed. The reddish precipitate in the creek starts right away at the source and contains up to 8 %(w/w) of arsenic. As shown in a previous publication [5] the arsenic is bound only weak to the iron hydroxides. A mobilization is possible by desorption without dissolution of the iron hydroxides. 

The oxidized form of As, arsenate, As(V), which is present as HAs04 at neutral pH (p f values in Table 7.8), is sorbed on soil surfaces in a similar way to orthophosphate. The reduced form arsenite, As(lll), which is present in solution largely as H3As03(p fi = 9.29), is only weakly sorbed, hence mobility tends to increase under reducing conditions. Mobility will also increase without reduction of As(V) because, as for phosphate, reductive dissolution of iron oxides results in desorption of HAs04 into the soil solution. Under prolonged submergence As(lll) may be co-precipitated with sulfides. 

Izumi, F. (1993) Rietveld analysis program RIE-TAN and PREMOS and special applications. In Young, R.A. (ed.) The Rietveld Method, Oxford, Oxford University Press, 236-253 Jackson, B.P. Miller, W.P. (2000) Effectiveness of phosphate and hydroxide for desorption of arsenic and selenium species from iron oxides. Soil Sci. Soc. Am. J. 64 1616-1622 Jain, A. Raven, K.P. Loeppert, R.EI. (1999) Ar-senite and arsenate adsorption on ferrihy-drite Surface charge reductions and net OEI-release stoichiometry. Environ. Sci. Techn. 

Lafferty, B.J. and Loeppert, R.H. (2005) Methyl arsenic adsorption and desorption behavior on iron oxides. Environmental Science and Technology, 39(7), 2120-27. 

Jackson, B.P. and Miller, W.P. (2000) Effectiveness of phosphate and hydroxide for desorption of arsenic and selenium species from iron oxides. Soil Science Society of America Journal, 64(5), 1616-22. 

Foley and Ayuso (2008) suggest that typical processes that could explain the release of arsenic from minerals in bedrock include oxidation of arsenian pyrite or arsenopyrite, or carbonation of As-sulfides, and these in general rely on discrete minerals or on a fairly limited series of minerals. In contrast, in the Penobscot Formation and other metasedimentary rocks of coastal Maine, oxidation of arsenic-bearing iron—cobalt— nickel-sulfide minerals, dissolution (by reduction) of arsenic-bearing secondary arsenic and iron hydroxide and sulfate minerals, carbonation and/or oxidation of As-sulfide minerals, and desorption of arsenic from Fe-hydroxide mineral surfaces are all thought to be implicated. All of these processes contribute to the occurrence of arsenic in groundwaters in coastal Maine, as a result of the variability in composition and overlap in stability of the arsenic source minerals. Also, Lipfert et al. (2007) concluded that as sea level rose, environmental conditions favored reduction of bedrock minerals, and that under the current anaerobic conditions in the bedrock, bacteria reduction of the Fe-and Mn-oxyhydroxides are implicated with arsenic releases. 

Water chemistry patterns in high arsenic wells are not consistent with other geochemical mechanisms of arsenic release. The positive correlation of high arsenic to sulfate and trace metals, and the negative correlation to pH, are not suggestive of desorption or dissolution of iron hydroxides. 

Desorption of arsenic from iron hydroxides is another potential cause of arsenic release, although the data do not indicate that it plays a significant role in the region. However, pH is slightly elevated in wells with low and moderate arsenic as compared with background ground water. Further research is needed to evaluate desorption as a potential mechanism for arsenic release. 

The first seven cycles of an in situ iron removal project in The Netherlands were simulated with the hydrogeochemical transport model PHREEQC (version 2). The concentration changes of CH4, NH/, Mn, Fe , P04 and As are discussed in detail. Arsenic shows concentration jumps in pumped groundwater which are related to oxidation/reduction and sorption/desorption reactions resulting from the water quality variations. 

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