Behavior of PBTC, HEDP, and aminophosphonates in the process of wastewater treatment

Ten times at intervals of 1–2 months, individual treatment stages of two wastewater treatment plants (WWTPs) were analyzed for the five quantitatively most widely used phosphonates. The total dissolved concentration of the investigated phosphonates in the influents was between 131 µg/L and 384 µg/L. The nitrogen-free phosphonates 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and 1-hydroxyethylidene(1,1-diphosphonic acid) (HEDP) accounted for an average proportion of 83–85%. Diethylenetriaminepenta(methylene phosphonic acid) (DTPMP) contributed with 13–14%, whereas aminotris(methylphosphonic acid) (ATMP) (≤15 µg/L) and ethylenediaminetetra(methylene phosphonic acid) (EDTMP) (≤11 µg/L) contents detected in the WWTP influents were comparatively low. The application of new analytical methods allowed the quantification of phosphonates in the solid fraction of the WWTP influents for the first time. High loads of phosphonates were determined (223–2555 mg/kg), indicating that 20%–80% of the phosphonates are present in the adsorbed state. The removal of total dissolved phosphonate by secondary clarification was between 69.7% and 92.4% (medians: 90.7% and 87.7%). In both WWTPs, HEDP (medians: 89.2% and 86.4%) was slightly better eliminated than PBTC (medians: 87.2% and 82.5%). In the sand filtration stage of a WWTP, the average removal was not further improved. In contrast, an additional removal of dissolved phosphonates could be achieved by activated carbon treatment (median: 96.4%). The proportion of phosphonate-P in the dissolved unreactive phosphorus fraction was consistently between 10% and 40% throughout all treatment stages

Detoxification of pesticide-containing wastewater with FeIII, activated carbon and Fenton reagent and its control using three standardized bacterial inhibition tests

Discharge of toxic industrial wastewaters into biological wastewater treatment plants may result in inhibition of activated sludge bacteria (ASB). In order to find an appropriate method of detoxification, the wastewater of a pesticide-processing plant in Vietnam was treated with three different methods (FeIII, powdered activated carbon (PAC), Fenton (FeII/H2O2)) analyzing the detoxification effect with the nitrification inhibition test (NIT), respiration inhibition test (RIT) and luminescent bacteria test (LBT). The heterotrophic ASB were much more resistant to the wastewater than the autotrophic nitrificants. The NIT turned out to be more suitable than the RIT since the NIT was less time-consuming and more reliable. In addition, the marine Aliivibrio fischeri were more sensitive than the nitrificants indicating that a lack of inhibition in the very practical and time-efficient LBT correlates with a lack of nitrification inhibition. With 95%, the Fenton method showed the highest efficiency regarding the chemical oxygen demand (COD) removal. Although similar COD removal (60–65%) was found for both the FeIII and the PAC method, the inhibitory effect of the wastewater was reduced much more strongly with PAC. Both the NIT and the LBT showed that the PAC and Fenton methods led to a similar reduction in the inhibitory effect

Removal of emerging contaminants and estrogenic activity from wastewater treatment plant effluent with UV/chlorine and UV/H2O2 advanced oxidation treatment at pilot scale

Effluent of a municipal wastewater treatment plant (WWTP) was treated on-site with the UV/chlorine (UV/HOCl) advanced oxidation process (AOP) using a pilot plant equipped with a medium pressure UV lamp with an adjustable performance of up to 1 kW. Results obtained from parallel experiments with the same pilot plant, where the state of the art UV/H2O2 AOP was applied, were compared regarding the removal of emerging contaminants (EC) and the formation of adsorbable organohalogens (AOX). Furthermore, the total estrogenic activity was measured in samples treated with the UV/chlorine AOP. At an energy consumption of 0.4 kWh/m3 (0.4 kW, 1 m3/h) and in a range of oxidant concentrations from 1 to 6 mg/L, the UV/chlorine AOP had a significantly higher EC removal yield than the UV/H2O2 AOP. With free available chlorine concentrations (FAC) in the UV chamber influent of at least 5 mg/L (11 mg/L of dosed Cl2), the total estrogenic activity could be reduced by at least 97%. To achieve a certain concentration of FAC in the UV chamber influent, double to triple the amount of dosed Cl2 was needed, resulting in AOX concentrations of up to 520 µg/L

Evaluation of Different Clinoptilolite Zeolites as Adsorbent for Ammonium Removal from Highly Concentrated Synthetic Wastewater

The supply of food to the growing world population requires an increasing amount of nitrogen fertilizers, which can be achieved both by the energy-intensive Haber–Bosch process and by recovering ammonium from wastewater. Within the scope of this work, it is investigated to what extent different clinoptilolites (CLIs) can be used as ion-exchangers for the removal of ammonium from highly concentrated solutions. To this end, finely ground CLIs with different grain sizes (EcoZeo 20 and CCP 20: 0–20 µm, Micro 200: 0–200 µm) were tested for their sorption properties by varying the parameters of the sorption solution (c0 = 1000 mg NH4-N/L) such as pH, temperature, or contact time. All three CLIs tested were effective at adsorbing ammonium. In a pH range from 2 to 8, all CLIs were able to eliminate ammonium equally well. Furthermore, a contact time of 60 min was sufficient to achieve 84–88% of the maximum load. At a temperature of 34 °C, the highest loading was achieved (investigated range: 10–34 °C), indicating that the adsorption process of all CLIs was exergonic and endothermic. Especially for wastewater streams with high ammonium concentrations such as sludge water from wastewater treatment plants, CLI proved to be suitable to adsorb ammonium

Influence of wastewater discharge on the occurrence of PBTC, HEDP, and aminophosphonates in sediment, suspended matter, and the aqueous phase of rivers

Sediment, suspended matter (SM), and water of a large river (Neckar; River1) and a small river (Körsch; River2) were analyzed for the phosphonates 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethylidene (1,1-diphosphonic acid) (HEDP), aminotris (methylphosphonic acid) (ATMP), ethylenediaminetetra (methylene phosphonic acid) (EDTMP), and diethylenetriaminepenta (methylene phosphonic acid) (DTPMP). Ten samplings were performed at intervals of one to two months during one year, each covering the relevant matrices before and behind the discharge point of a wastewater treatment plant (WWTP). In River1, the total concentration of dissolved phosphonate did not change significantly (2.4–5.8 µg/L before vs. 2.5–6.6 µg/L behind WWTP; p = 0.9360). In River2, it increased significantly from 2000 mg/kg phosphonate loads. In general, the nitrogen-free phosphonates PBTC and HEDP were most predominant in both dissolved and adsorbed form, of which HEDP had the highest adsorption affinity

Application of Natural Clinoptilolite for Ammonium Removal from Sludge Water

Sludge water (SW) arising from the dewatering of anaerobic digested sludge causes high back loads of ammonium, leading to high stress (inhibition of the activity of microorganisms by an oversupply of nitrogen compounds (substrate inhibition)) for wastewater treatment plants (WWTP). On the other hand, ammonium is a valuable resource to substitute ammonia from the energy intensive Haber-Bosch process for fertilizer production. Within this work, it was investigated to what extent and under which conditions Carpathian clinoptilolite powder (CCP 20) can be used to remove ammonium from SW and to recover it. Two different SW, originating from municipal WWTPs were investigated (SW1: c0 = 967 mg/L NH4-N, municipal wastewater; SW2: c0 = 718–927 mg/L NH4-N, large industrial wastewater share). The highest loading was achieved at 307 K with 16.1 mg/g (SW1) and 15.3 mg/g (SW2) at 295 K. Kinetic studies with different specific dosages (0.05 gCLI/mgNH4-N), temperatures (283–307 K) and pre-loaded CCP 20 (0–11.4 mg/g) were conducted. At a higher temperature a higher load was achieved. Already after 30 min contact time, regardless of the sludge water, a high load up to 7.15 mg/g at 307 K was reached, achieving equilibrium after 120 min. Pre-loaded sorbent could be further loaded with ammonium when it was recontacted with the SW

Recovery of Ammonium Sulfate Solution by Regeneration of Loaded Clinoptilolite

The zeolite clinoptilolite (CLI) is known to be a very good ion exchanger, as it consists of a three-dimensional structure formed of AlO4− and SiO4 tetrahedral, which are connected by a common oxygen atom. The micropores formed by this structure (with free diameters in the range of 0.40 nm and 0.72 nm) are fine enough to allow cations and water molecules to enter and be exchanged. CLI is a suitable, inexpensive, and globally available material for removing ammonium from highly-concentrated wastewater and is proven to be selective in ammonium uptake and regeneration since no effect of the provenance of the ammonium (matrix-free NH4Cl solution or sludge water) could be found. However, regeneration of the clinoptilolite is necessary to recover the adsorbed ammonium for further use and restore its capability for ion exchange. Within this work, the method by which clinoptilolite, loaded with ammonium (q = 8.1–16.6 mg/g) from different sludge waters and ammonium chloride solution, can be regenerated to yield a stoichiometric ammonium sulfate solution (ASS), that could be used, e.g., as a fertilizer, was investigated. A regeneration solution containing Na2SO4 (0.25 n(Na2SO4)/n(NH4+ads)) with a varying NaOH ratio (0–2.14 n(NaOH)/n(NH4+ads)) was tested. To obtain a high ammonium concentration in the eluate, a large mass fraction ω of 284 g/kg of CLI in the regeneration solution was applied. The effects of different ammonium loads, different origins of the ammonium, and residual moisture on the necessary components of the regeneration solution, in which an ASS is obtained within a contact time of 10 min at 22 °C, were studied. A stoichiometric ASS from CLI loaded up to a maximum of 13.5 mg/g was obtained with a mixture of 0.25 n(Na2SO4)/n(NH4+ads) together with 0.8–1.0 n(NaOH)/n(NH4+ads) for dry CLI, and 0.75 n(NaOH)/n(NH4+ads) for CLI with residual moisture

Correction: Wasielewski, S., et al. Evaluation of Different Clinoptilolite Zeolites as Adsorbent for Ammonium Removal from Highly Concentrated Synthetic Wastewater. Water 2018, 10, 584

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Influence of Ammonium Ions, Organic Load and Flow Rate on the UV/Chlorine AOP Applied to Effluent of a Wastewater Treatment Plant at Pilot Scale

This work investigates the influence of ammonium ions and the organic load (chemical oxygen demand (COD)) on the UV/chlorine AOP regarding the maintenance of free available chlorine (FAC) and elimination of 16 emerging contaminants (ECs) from wastewater treatment plant effluent (WWTE) at pilot scale (UV chamber at 0.4 kW). COD inhibited the FAC maintenance in the UV chamber influent at a ratio of 0.16 mg FAC per mg COD (kHOCl–COD = 182 M−1s−1). An increase in ammonium ion concentration led to a stoichiometric decrease of the FAC concentration in the UV chamber influent. Especially in cold seasons due to insufficient nitrification, the ammonium ion concentration in WWTE can become so high that it becomes impossible to achieve sufficiently high FAC concentrations in the UV chamber influent. For all ECs, the elimination effect by the UV/combined Cl2 AOP (UV/CC) was not significantly higher than that by sole UV treatment. Accordingly, the UV/chlorine AOP is very sensitive and loses its effectiveness drastically as soon as there is no FAC but only CC in the UV chamber influent. Therefore, within the electrical energy consumption range tested (0.13–1 kWh/m3), a stable EC elimination performance of the UV/chlorine AOP cannot be maintained throughout the year