Tobias David Reinhardt

Phosphonates are widely used in various industries. It is desirable to remove them before discharging phosphonate-containing wastewater. This study describes a large number of batch experiments with adsorbents that are likely suitable for the removal of phosphonates. For this, adsorption isotherms for four different granular ferric hydroxide (GFH) adsorbents were determined at different pH values in order to identify the best performing material. Additionally, the influence of temperature was studied for this GFH. A maximum loading for nitrilotrimethylphosphonic acid (NTMP) was found to be $\sim$12 mg P/g with an initial concentration of 1 mg/L NTMP-P and a contact time of 7 days at room temperature. Then, the adsorption of six different phosphonates was investigated as a function of pH. It was shown that GFH could be used to remove all investigated phosphonates from water and, with an increasing pH, the adsorption capacity decreased for all six phosphonates. Finally, five adsorption-desorption cycles were carried out to check the suitability of the material for multiple re-use. Even after five cycles, the adsorption process still performed well.

This paper introduces a procedure to investigate the adsorption of phosphonates onto iron-containing filter materials, particularly granular ferric hydroxide (GFH), with little effort and high reliability. The phosphonate, e.g., nitrilotrimethylphosphonic acid (NTMP), is brought into contact with the GFH in a rotator in a solution buffered by an organic acid (e.g., acetic acid) or Good buffer (e.g., 2-(N-morpholino)ethanesulfonic acid) MES and N-cyclohexyl-2-hydroxyl-3-aminopropanesulfonic acid CAPSO) in a concentration of 10 mM for a specific time in 50 mL centrifuge tubes. Subsequently, after membrane filtration (0.45 µm pore size), the total phosphorus (total P) concentration is measured using a specifically developed determination method (ISOmini). This method is a modification and simplification of the ISO 6878 method: a 4 mL sample is mixed with H2SO4 and K2S2O8 in a screw cap vial, heated to 148-150 °C for 1 h and then mixed with NaOH, ascorbic acid and acidified molybdate with antimony(III) (final volume of 10 mL) to produce a blue complex. The color intensity, which is linearly proportional to the phosphorus concentration, is measured spectrophotometrically (880 nm). It is demonstrated that the buffer concentration used has no significant effect on the adsorption of phosphonate between pH 4 and 12. The buffers, therefore, do not compete with the phosphonate for adsorption sites. Furthermore, the relatively high concentration of the buffer requires a higher dosage concentration of oxidizing agent (K2S2O8) for digestion than that specified in ISO 6878, which, together with the NaOH dosage, is matched to each buffer. Despite the simplification, the ISOmini method does not lose any of its accuracy compared to the standardized method.