Arsenic Adsorption on Iron Oxides in the Presence of Soluble Organic Carbon and the Influence of Arsenic on Radish and Lettuce Development

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Virginia Tech

Chapter 2: Germination and Growth of Radish (Raphanus sativus) and Lettuce (Lactuca sativus) Exposed to Arsenite and Arsenate in Hydroponic Growth Solution

Little information is available on the survival, uptake, and dry mass production of vegetable seedlings and maturing plants in arsenic enriched environments. Such information is however very important to many vegetable growers in areas of subsistent agricultural like Bangladesh or home-gardeners in closer proximity of As sources such as metal smelters.

Accordingly we conducted research investigating (i) the germination and radical formation of radish and lettuce seeds at varying As (V) and As (III) concentrations and (ii) radish and lettuce plants in solution culture. Seed germination studies demonstrated that 0.1mM and 0.025mM are toxic threshold levels of As (III and V) for radishes and lettuce, respectively, while As (V) is more toxic to radish seeds than As (III). Arsenic (III and V) impacted both germination and radical development in radish seeds. For lettuce we observed that As had no impact on germination but reduced radical length significantly (p < 0.01). At most equimolar concentrations, As (III) was more toxic than As (V) in lettuce seeds (0.025 - 0.10mM As), a result contrary to those obtained in radish seeds (0.05 - 0.5mM As). The hydroponic growth studies showed that losses and increases in dry weight are a function of absorbed As and are dependent on the source of As: As (V) or As (III). Moreover, the effect of absorbed As (V) or As (III) on dry weight reductions and increases differed between root and shoot portions of the plants and are crop dependent. Tissue-As (originally solution As (V)) was more toxic at the radish root level and tissue-As (originally solution As (III)) was more toxic at the radish shoot level. Conversely for lettuce, As (III) caused reductions in dry weight, while As (V) had a stimulating effect on biomass production. Lower As (V) concentrations in plant tissue throughout the lettuce study and at low As (V) concentrations (0.02mM) in the radish study may be explained by the molar ratio of P:As of approximately 5. From a food nutrition safety standpoint, studies need to concentrate on sub-lethal levels in order to ensure the proper formation of the harvestable portion of the plant.

Chapter 3: Adsorption of Arsenate (V) and Arsenite (III) on Goethite in the Presence and Absence of Soluble Organic Carbon

The environmental fate of arsenic is of utmost importance as the U.S. EPA has recently proposed to tighten the arsenic drinking water standard from 50 ppb to 5 ppb. In natural systems the presence of dissolved organic carbon (DOC) may compete with As for adsorption to mineral surfaces, hence increasing its potential bioavailability. Accordingly, the adsorption of arsenate As (V) and As (III) on goethite (α-FeOOH) was investigated in the presence of either a peat humic acid (Hap), a Suwannee River Fulvic Acid (FA) (IHSS) or citric acid (CA). Adsorption edges and kinetic experiments were used to examine the effects of equimolar concentrations of organic adsorbates on arsenic adsorption. Adsorption envelopes were conducted over a pH range of 11 to 3, while the kinetic studies were conducted at pH 6.5 for As (V) and pH 5.0 for As (III). Arsenate adsorption was inhibited in the order of Hap > FA > CA while arsenite adsorption was inhibited in the order of CA > FA > Hap. Humic acid reduces As V adsorption starting at pH 9, with a maximum reduction at pH 6.5. Fulvic acid slightly inhibited As (V) adsorption starting at pH 5, and this inhibition increased with a decrease in pH. No effect was observed in the presence of CA. Arsenite adsorption is inhibited by HA starting a pH 7 and increases with a decrease in pH, while FA and CA reduce As (III) adsorption beginning at pH 8, with a continuous reduction as the pH decreases. The differential extent of As V adsorption in the presence of the organic acids suggests that the distribution and the respective densities of the abundant functional groups (phenol/ catechol OH or COO⁻) are significant in the adsorption of As (V). Furthermore, larger organic acids may hydrophobically partition to surfaces via a more favorable entropy driven reaction mechanism which may influence As (V) diffusion and its subsequent adsorption to surfaces. The decrease in As (III) adsorption is caused by its reduced affinity for the surface at pH values lower than 9, and the simultaneous increase in surface activity by the organic substances' via their COO⁻ functional groups. The results of these experiments suggests that dissolved organic carbon substances are capable of increasing the bioavailability of As in soil and water systems in which the dominant solid phase is a crystalline iron oxide.

Chapter 4: Adsorption of Arsenate and Arsenite on Ferrihydrite in the Presence and Absence of Dissolved Organic Carbon (DOC)

The adsorption of As (V) and As (III) on synthetic 2-line ferrihydrite in the presence and absence of a peat humic acid (Hap), Suwannee River Fulvic Acid (FA) or citric acid (CA) was investigated. Previous work with goethite has demonstrated the ability of DOC materials to reduce As (V) and As (III) adsorption. In this study, a batch technique was used to examine the adsorption of arsenic (III and V) and DOCs on ferrihydrite in the pH range from 3 to 11. The results obtained demonstrated that As (V) adsorption on ferrihydrite was reduced only in the presence of CA. Arsenate reduced the adsorption of all organic acids except Hap. Both FA and CA reduced As (III) adsorption on ferrihydrite, while Hap had no effect. Fulvic and citric acid adsorption on ferrihydrite was reduced in the presence of As (III), however, adsorption increases of FA and CA were observed at lower pH, which is consistent with a decrease in As(III) adsorption. The peat humic acid had no effect on As (III) adsorption, and we believe that the adsorption process of Hap and As (III and V) on ferrihydrite are independent of each other. The observed differences between this study and the study on goethite are believed to be an intricate function of ferrihydrite's surface characteristics, which affects the mechanisms of surface adsorption and hence the affinity of organic acids such as Hap, FA, and CA for the ferrihydrite surface. As such, the adsorption of DOCs to ferrihydrite are assumed to be energetically less favorable and to occur with a fewer number of ligands, resulting in lower surface coverage of weaker bond strength. Additional factors for the observed differences are discussed. This work demonstrates the importance of the solid phase in adsorption processes and functional group composition, as noticeable differences are observed in comparison to a crystalline Fe-oxide solid phase.

As (V), As (III), competition, fulvic acid, humic acid, amorphous, citric acid