As(III) removal in rapid filters: Effect of pH, Fe(II)/Fe(III), filtration velocity and media size.

In the top layer of aerated rapid sand filtration systems, uncharged As(III) is biologically converted to charged As(V). Subsequently, the main removal mechanism for As(V) is adsorption onto oxidised, flocculated Fe(III) (hydrous ferric hydroxides; HFO). The aim of this research was to understand the interactions between As and Fe in biologically active rapid filter columns and investigate the effect of different operational modes on Fe removal to subsequently promote As removal. For this purpose, different filter media column experiments were performed using natural, aerated groundwater containing 3.4 µg/l As(III). Results show that independent of the filter media size, complete (biological) conversion of As(III), manganese, ammonium and nitrite was achieved in approximately 70 days. After ripening, enhanced As removal was achieved with a top layer of coarse media or by dosing additional Fe(III). Addition of Fe(II) did not have the same effect on As removal, potentially due to heterogeneous Fe(II) oxidation in the upper layer of the filter, attaching rapidly to the filter grain surface and thereby preventing HFO flocs to penetrate deeper into the bed. Increasing the flow rate from 1 to 4 m/h did not improve As removal and lowering the pH from 8 to 7.4, resulted in an 55% increased removal of dissolved As. Altogether it is concluded that As removal in biologically active rapid sand filters can be improved by applying coarser filter media on top, in combination with dosing Fe(III) and/or pH correction.

Effect of supernatant water level on As removal in biological rapid sand filters.

Current groundwater treatment facilities, mostly relying on aeration-filtration configurations, aim at the removal of iron (Fe), ammonia (NH4 +) and manganese (Mn). However, recently water companies expressed the ambition to also reduce arsenic (As) concentrations in these rapid sand filters. The aim of this study was to investigate the effect of the Fe oxidation state entering a biological filter bed on As removal. By varying supernatant water level, either Fe(II) or Fe(III) in the form of hydrous ferric oxides (HFO) could be stimulated to enter the filter bed at alkaline groundwater pH (7.6). The experimental pilot column filters showed that once the As(III) oxidation stabilised in the top layer of the filter sand, As removal reached its maximum (±75% at 120 cm supernatant level and 1.5 m/h filtration velocity). The increase in supernatant level from 5 to 120 cm resulted in additional HFO production prior to rapid filtration (1.5, 5 and 10 m/h), i.e. homogeneous Fe(II) oxidation and flocculation, and subsequently, HFO ending up deeper into the filter bed (120 cm filter depth). At a low supernatant water level of 5 cm, Fe(II) oxidised heterogeneously and was removed within the top 20 cm of the filter bed. Consequently, filters with high supernatant levels removed As to lower levels (by 20%) than in filters with low supernatant water levels. The benefits of Fe(II) oxidation prior to filtration for As removal was confirmed by comparing Fe(III) to Fe(II) additions in the supernatant water or in the filter bed. Overall it is concluded that in biological groundwater filters, the combination of a higher supernatant level and/or Fe(III) addition with biological As(III) oxidation in the top of the filter bed promotes As removal.

As(III) oxidation by MnO2 during groundwater treatment.

The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO2), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO2 powder was a very pure - commercially available - natural MnO2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO2 surface (at pH 7). Therefore it is concluded that just because MnO2 is present in a filter bed, it does not necessarily mean that MnO2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides.

Fate of low arsenic concentrations during full-scale aeration and rapid filtration.

In the Netherlands, groundwater treatment commonly consists of aeration, with subsequent sand filtration without using chemical oxidants like chlorine. With arsenic (As) concentrations well below the actual guidelines of 10 µg As/L, groundwater treatment plants have been exclusively designed for the removal of iron (Fe), manganese and ammonium. The aim of this study was to investigate the As removal capacity at three of these groundwater treatment plants (10-26 µg As/L) in order to identify operational parameters that can contribute to lowering the filtrate As concentration to <1 µg/L. For this purpose a sampling campaign and experiments with supernatant water and hydrous ferric oxide (HFO) flocs were executed to identify the key mechanisms controlling As removal. Results showed that after aeration, As largely remained mobile in the supernatant water; even during extended residence times only 20-48% removal was achieved (with 1.4-4.2 mg/L precipitated Fe(II)). Speciation showed that the mobile As was in the reduced As(III) form, whereas, As(V) was readily adsorbed to the formed HFO flocs. In the filter bed, the remaining As(III) completely oxidized within 2 min of residence time and As removal efficiencies increased to 48-90%. Filter grain coating analysis showed the presence of manganese at all three treatment plants. It is hypothesized that these manganese oxides are responsible for the accelerated As(III) oxidation in the filter bed, leading to an increased removal capacity. In addition, pH adjustment from 7.8 to 7.0 has been found to improve the capacity for As(V) uptake by the HFO flocs in the filter bed. The overall conclusion is, that during groundwater treatment, the filter bed is crucial for rapid As(III) removal, indicating the importance to control the oxidation sequence of Fe and As for improved As removal efficiencies.