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Applying Natural and K-Enriched Zeolite Before Struvite Precipitation Improved the Recovery of NH4+ from Liquid Digestate and the Reagent Use Efficiency

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Abstract

Implementing nutrient recycling in wastewater treatment plants is essential for sustainable agriculture. In this study, we investigated a biphasic treatment system for anaerobic liquid digestate, which involved natural and K-enriched zeolite for NH4+ recovery (phase 1), followed by struvite crystallization under two conditions: NH4+ excess and Mg2+ excess (phase 2). The adsorption of NH4+ by natural zeolite enabled saving Mg and P reagents, used to achieve target Mg:NH4:PO4 ratios. The reagent use efficiency of struvite precipitation was highest with natural zeolite under NH4+ excess conditions (96%), whereas the other treatments exhibited lower yields. In this condition, the digestate enriched in Ca2+ released by zeolite; however, no P interferences occurred (Ca2+/Mg2+  < 0.5). Fractions of Ca2+ precipitated as CaCO3. Both the isomorphic NH4- and K-struvite occurred, distinguished by calibrating XRPD data (total struvite) with N contents (indicative of NH4+-struvite). The precipitates comprised NH4- and K-struvite at 60% and 30% (calcite at 9%) in the treatment that involved natural zeolite, 65% and 35% with the K-exchanged zeolite, due to higher presence of K+. Concerning the chemical evolution of the treated digestate, fewer alterations occurred for inorganic ions in the treatment that involved natural zeolite (phase 1) with NH4+ excess condition (phase 2), besides for unreacted SO42– derived from the Mg reagent. The recovered zeolite was enriched in N at 0.5%. Struvite precipitates met the EU regulations regarding permissible levels of organic C, P content, and heavy metal impurities, thereby potentially enabling its use as a fertilizer.

Highlights

  • Zeolites allowed less reagents for reaching optimum struvite precipitation.

  • N loads were reduced with zeolite–struvite treatment up to 86%.

  • Struvite from digestate is usable in agriculture and complied with EU regulations.

  • The precipitation of K-struvite limited the recovery of N from digestate.

  • To discern (K) and (NH4)-struvite, XRD must be combined with chemical information.

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Data Availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

Abbreviations

NZT :

Natural chabazite zeolitic tuff

KZT :

K-enriched chabazite zeolitic tuff

NZT-S:

Treatment using NZT in combination with struvite

KZT-S:

Treatment using KZT in combination with struvite

CNTR:

Conventional struvite precipitation without using zeolitic tuff

MR1:

Molar ratio 1 (Mg:NH4:PO4 = 1:1.5:1)

MR2:

Molar ratio 2 (Mg:NH4:PO4 = 2:1:1)

EA-IRMS:

Elemental analyzer coupled with an isotopic ratio mass spectrometer

EC:

Electrical conductivity

ICP-MS:

Inductively coupled plasma mass spectrometry

SEM-EDS:

Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy

XRPD:

X-ray powder diffraction

C e.tg :

NH4+-N equilibrium target concentration (target concentration for a single zeolitic tuff adsorption batch)

T r :

Theoretical NH4+-N recovery

A r :

Actual NH4+-N recovery

R % :

NH4+-N recovery efficiency—parameter used to evaluate the efficiency of reagents use

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Acknowledgements

The authors thank Azienda Agricola Minghini (San Biagio, Ferrara, Italy) for the furniture of liquid digestate. We also thank Dr. Renzo Tassinari for performing the ICP-MS analyses, Dr. Umberto Tessari for the particle size analyses, Dr. Nicola Tescaro for help during the preliminary studies, and Prof. Carmela Vaccaro for supporting the research.

Funding

Founded by PNRR–M4C2INV1.5, NextGenerationEU-Avviso 3277/2021 -ECS_00000033-ECOSISTER-spk1.

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Authors and Affiliations

Authors

Contributions

Galamini G. and Ferretti G. contributed to conceptualization and methodology; Galamini G., Ferretti G., Medoro V., Eftekhari N., and Favero M. did formal analysis; Galamini G. was involved in investigation, data curation, and writing––original draft; Ferretti G., Faccini B., and Coltorti M. were involved in writing––review; Coltorti M. performed supervision.

Corresponding author

Correspondence to Giacomo Ferretti.

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The authors declare that there are no competing interests with this work on behalf of all coauthors.

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Galamini, G., Ferretti, G., Medoro, V. et al. Applying Natural and K-Enriched Zeolite Before Struvite Precipitation Improved the Recovery of NH4+ from Liquid Digestate and the Reagent Use Efficiency. Int J Environ Res 18, 44 (2024). https://doi.org/10.1007/s41742-024-00595-5

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  • DOI: https://doi.org/10.1007/s41742-024-00595-5

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