XAS evidence of As(V) association with iron oxyhydroxides in a contaminated soil at a former arsenical pesticide processing plant.
The molecular-level speciation of arsenic has been determined in a soil profile in the Massif Central near Auzon, France that was impacted by As-based pesticides by combining conventional techniques (XRD, selective chemical extractions) with X-ray absorption spectroscopy (XAS). The arsenic concentration is very high at the top (>7000 mg kg(-1)) and decreases rapidly downward to a few hundreds of milligrams per kilogram. A thin layer of schultenite (PbHAsO4), a lead arsenate commonly used as an insecticide until the middle of the 20th century, was found at 10 cm depth. Despite the occurrence of this As-bearing mineral, oxalate extraction indicated that more than 65% of the arsenic was released upon dissolution of amorphous iron oxides, suggesting a major association of arsenic with these phases within the soil profile. Since oxalate extraction cannot unambiguously distinguish among the various chemical forms of arsenic, these results were confirmed by a direct in situ determination of arsenic speciation using XAS analysis. XANES data indicate that arsenic occurs mainly as As(V) along the soil profile except for the topsoil sample where a minor amount (7%) of As(III) was detected. EXAFS spectra of soil samples were fit by linear combinations of model compounds spectra and by a shell-by-shell method. These procedures clearly confirmed that As(V) is mainly (at least 80 wt %) associated with amorphous Fe(III) oxides as coprecipitates within the soil profile. If any, the proportion of schultenite, which was evidenced by XRD in a separate thin white layer, does not account for more than 10 wt % of arsenic in soil samples. This study emphasizes the importance of iron oxides in restricting arsenic dispersal within soils following dissolution of primary As-bearing solids manufactured for use as pesticides and released into the soils.
Cancès
B
B
Institut de Minéralogie et de Physique des Milieux Condenses, UMR CNRS 7590, 140 rue de Lourmel, 75015 Paris, France.
Juillot
F
F
Morin
G
G
Laperche
V
V
Alvarez
L
L
Proux
O
O
Hazemann
J L
JL
Brown
G E
GE
Calas
G
G
D001151:Arsenic / Q000032:analysis / Q000737:chemistry*; D001152:Arsenicals / Q000737:chemistry; D005290:Ferric Compounds / Q000032:analysis / Q000737:chemistry*; D006256:Hazardous Waste; D007501:Iron / Q000737:chemistry; D010575:Pesticides / Q000737:chemistry; D012989:Soil Pollutants / Q000032:analysis* / Q000633:toxicity; D013052:Spectrometry, X-Ray Emission; D014874:Water Pollutants, Chemical / Q000633:toxicity
D001152:Arsenicals; D005290:Ferric Compounds; D006256:Hazardous Waste; D010575:Pesticides; D012989:Soil Pollutants; D014874:Water Pollutants, Chemical; C021024:ferric hydroxide; D007501:Iron; D001151:Arsenic