Supporting Information. Selenium Removal from Sulfate-Containing Ground Water Using. Granular Layered Double Hydroxide Materials

Transcription

1 Supporting Information Selenium Removal from Sulfate-Containing Ground Water Using Granular Layered Double Hydroxide Materials Man Li 1, Lisa M. Farmen 2, Candace K. Chan 1 * 1. Materials Science and Engineering, School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ 85287; *candace.chan@asu.edu 2. Crystal Clear Technologies, Inc., 2828 SW Corbett, Suite 145, Portland, OR Materials and Reagents Granular LDH was obtained from Sasol Germany GmbH (PURALOX MG 63 HT Granulate) with a reported median particle diameter of 1.46 mm. For evaluation in jar tests, the granular LDH was used as received. For column tests, the granular LDH was gently ground into small particles using a mortar and a pestle. Particles ranging in size between µm were obtained using sieves (mesh No. 35 and No. 60). A powdered LDH was obtained from (Sigma- Aldrich (Hydrotalcite synthetic, product no ) to use as a reference sample for materials characterization. Synthetic water samples were prepared from ultrapure de-ionized (DI) water (18.2 MΩ, ph 5.5) spiked with selenium. Stock solutions (1000 ppm) of selenate, Se(VI), and selenite, Se(IV), were prepared by dissolving Na 2 SeO 4 (Sigma-Aldrich, product no G, purity 98.0%) or NaHSeO 3 (Sigma-Aldrich, product no. S G, purity 98) into DI water. S1

2 Groundwater was obtained from Salt River Project s Santan Generating Station, a combined cycle, natural-gas-powered plant in Gilbert, AZ. The boiler and cooling water for the Santan Generation Station are sourced from onsite wells or surface waters. Groundwater in the Salt River Project (SRP) service area contains naturally occurring levels of selenium, which can become concentrated in cooling tower water blowdown. Groundwater samples from one of the wells comprising the make-up water of cooling tower were obtained. Barium chloride pre-treatment of the well water prior to exposure to the LDH sorbent was investigated. A 1 M BaCl 2 solution (Sigma-Aldrich, product no L-R) was added to the water matrix using a 3:1 mol ratio of Ba 2+ to SO 2-4. Materials Characterization X-ray diffraction (XRD) characterization was performed using monochromatic Cu kα radiation (λ= Å) (Panalytical X pert Pro). Scanning electron microscopy (SEM) was performed with a Nova 200 NanoLab (FEI) focused ion beam. The sample was coated using Au sputtering for 45 s before use. The specific surface area of the samples was obtained using the Brunauer-Emmett-Teller (BET) method using nitrogen adsorption at 77 K nitrogen (Micromeritics TriStar II 3020). Fourier transform infrared (FTIR) spectra of samples were collected over the wavenumber range cm -1 on a Bruker IFS66V/S FTIR spectrometer in the ATR-FTIR mode using a diamond ATR sample module. Analysis of Selenium Concentrations in Water Spiked water samples were filtered using a 0.2 micron Isopore track etched polycarbonate membrane in a Pall syringe filter. Then, 2% nitric acid was added to the filtered sample solution for analysis of total selenium concentrations with inductively coupled plasma optical emission S2

3 spectroscopy (ICP-OES, ICAP-6300, Thermo Co., USA). For solutions spiked with 100 ppm selenate, the water was diluted 50X prior to ICP-OES analysis. Water samples from the column test effluent had low-level Se concentrations and were analyzed using inductively coupled plasma mass spectrometry (ICP-MS, icap Q quadrupole, Thermo Co., USA). The sulfur signal from ICP-MS was used to estimate the sulfate concentration in the acidified water solutions used for selenium analysis. Jar Testing Procedures Selenium removal tests were performed at room temperature using sorbents at a dosage of 1 g/l with sampling performed after different time periods. For jar tests comparing the trace level Se(VI) vs. high level Se(VI), the LDH media were evaluated in water samples that were agitated using a compact digital mini rotator (Thermo Scientific, Catalog no ) shaking at 300 rpm. The performance of the as-obtained LDH media (confirmed to have the nonlayered, periclase structure by XRD) was evaluated by spiking DI water to the desired Se(VI) level and shaking overnight prior to the initial sampling point at 0 min to establish the baseline [Se] level. Then, the as-obtained LDH was added to the DI water solution and water samples were taken at different time points. To evaluate the performance of LDH with the layered structure, the as-obtained LDH was immersed in DI water and agitated with the mini rotator overnight so that the layered structure could be reconstructed. Then, the appropriate amount of Se(VI) was added to the solution and the first sample was taken after 2 minutes. As the spiking procedure was the same for the asobtained LDH and the layered LDH, the initial Se levels are assumed to be the same. S3

4 For jar tests conducted in spiked groundwater, the sorbents were added to the water solutions and stirred at a constant speed with a magnetic stirrer. Water samples were prepared by spiking 100 ppm Se(VI) in the groundwater. Pretreated water samples were prepared using BaCl 2 with a Ba to S mol ratio of 3:1, and then spiking 100 ppm Se(VI). Column Testing Procedures Small scale column tests (Westerhoff et al., 2005)(Badruzzaman et al., 2004) were performed in a 1.1 cm diameter column 30 cm in height (Ace Glass) with Teflon end caps. Figure S1 shows a photograph of the column setup. The sorbent media (granular LDH) was immersed in DI water to remove any air before packing and to allow for media expansion. The sorbent bed was packed in the middle one-third of the column. Glass wool (Sigma-Aldrich) was placed above and below the media bed as well as in both ends of column as a support and to retain all of the sorbent media inside the column. Glass beads (Ace Glass, 5 mm diameter) were placed on either side of the glass wool to better disperse the influent flow. The glass wool and glass beads were pre-heated at 500 o C for 1 h in air to remove any contaminants and immersed in DI water before use. After packing the column, backwashing was performed using DI water to remove fine particles in countercurrent (upflow) mode until the effluent water ran clear. The empty bed contact time (EBCT) was 30 min. A peristaltic pump (NE-9000G, New Era Pump Systems) was used to set the flow rate to 0.3 ml/min according to the bed volume and desired EBCT. Test waters were pumped with upflow mode to avoid channeling. The well water provided by Salt River Project was used as the water matrix and was used as-obtained (not spiked) or with BaCl 2 pretreatment. Sampling time periods were performed approximately every 2 hours. After the column test, the sorbent was removed and dried at 50 o C for one week and the mass measured for calculation of the selenate capacity. S4

5 The exhaustion capacity Q e (µg/g) of the sorbent was calculated using Equation (S1) where C 0 (ppm) is the initial Se(VI) concentration in the influent; C (ppm) is the Se(VI) concentration in the effluent after leaving the column; m (g) is the dried sorbent bed mass in the column; and V e is the water volume (L) that was treated at exhaustion (Chubar and Szlachta, 2015). Q e = V = Ve (C 0- C)dV e V = 0 m (S1) In this work, Q e was estimated from the breakthrough curve as illustrated in Figure S2. The adsorbent exhaustion rate (AER) can be estimated as shown in Equation (S2) (Chubar and Szlachta, 2015). AER = m V e (7) S5

6 Supporting Figures Figure S1. Photograph of column test setup. Figure S2. Method used to estimate exhaustion capacity (Q e ) from column test breakthrough curve using the area of the blue shaded region below C 0. The total area is equal to the area of the rectangle (Area a) + the area of the triangle (Area b), in which Area a = C 0 V b ; Area b = 1 C 2 0 (V e V b ). V b is the volume of water that passed through the column until breakthrough and V e is the water volume that was treated at exhaustion. Q b also can be estimated as Area a. S6

7 Figure S3. SEM image of granular LDH; particles obtained after sonication shown in inset. Figure S4. Removal of 1 ppm selenite and selenate from DI water in jar test using granular LDH at 5 g/l S7

8 Figure S5. Jar test results using 1 g/l LDH in DI water spiked with (a) 3.43 ppb, (b) 72.9 ppm Se(VI) over long exposure times. The as-obtained LDH had the nonlayered, periclase structure. The layered LDH was obtained by reconstructing the as-obtained LDH in DI water. S8

9 References: Badruzzaman, M., Westerhoff, P., Knappe, D.R.U., Intraparticle diffusion and adsorption of arsenate onto granular ferric hydroxide (GFH). Water Res. 38, doi: /j.watres Chubar, N., Szlachta, M., Static and dynamic adsorptive removal of selenite and selenate by alkoxide-free sol-gel-generated Mg-Al-CO3 layered double hydroxide: Effect of competing ions. Chem. Eng. J. 279, doi: /j.cej Westerhoff, P., Highfield, D., Badruzzaman, M., Yoon, Y., Rapid small-scale column tests for arsenate removal in iron oxide packed bed columns. J. Environ. Eng. 131, doi: /(asce) (2005)131:2(262) S9