Abstract
Eutrophication can be caused by excessive input of nutrients, such as nitrate and phosphate, to surface water. Nutrients in groundwater can enter surface water by means of base flow, requiring treatment before they reach surface water bodies. While some studies have attempted to remove nitrate and phosphate, methods for simultaneous removal in groundwater have rarely been reported. In this study, we propose an innovative treatment method to simultaneously remove nitrate and phosphate in groundwater based on an injection of Ca-citrate complex. A total of five batch experiments with different conditions were conducted to identify the removal mechanisms of nitrate and phosphate and to evaluate the use of alternative organic materials, such as lactate. The results showed that Ca-citrate complex can remove nitrate and phosphate simultaneously. Nitrate was removed through denitrification by denitrifying bacteria which used citrate as a carbon source. The removal mechanisms for phosphate were precipitation of phosphate minerals (e.g., hydroxyapatite) and adsorption. The results also showed that reactive materials based on Ca-lactate complex were able to remove nitrate and phosphate. This study suggests that nitrate and phosphate in groundwater can simultaneously be removed using organic-based calcium complexes, proposing a promising remedial method to alleviate potential eutrophication in surface water as well as groundwater contamination.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Ahn J-H, Choo K-H, Park H-S (2008) Reverse osmosis membrane treatment of acidic etchant wastewater: effect of neutralization and polyelectrolyte coating on nitrate removal. J Membr Sci 310:296–302. https://doi.org/10.1016/j.memsci.2007.11.010
Allred BJ, Martinez LR, Gamble DL (2017) Phosphate removal from agricultural drainage water using an iron oxyhydroxide filter material. Water Air Soil Pollut 228:240. https://doi.org/10.1007/s11270-017-3410-9
Barca C, Gérente C, Meyer D, Chazarenc F, Andrès Y (2012) Phosphate removal from synthetic and real wastewater using steel slags produced in Europe. Water Res 46:2376–2384. https://doi.org/10.1016/j.watres.2012.02.012
Bazin H, Bouchu A, Descotes G, Petit-Ramel M (1995) Comparison of calcium complexation of some carboxylic acids derived from D-flucose and D-fructose. Can J Chem 73:1338–1347. https://doi.org/10.1139/v95-165
Benson VS, VanLeeuwe JA, Sanchez J, Dohoo IR, Somers GH (2006) Spatial analysis of land use impact on ground water nitrate concentrations. J Environ Qual 35:421–432. https://doi.org/10.2134/jeq2005.0115
Berkessa YW, Mereta ST, Feyisa FF (2019) Simultaneous removal of nitrate and phosphate from wastewater using solid waste from factory. Appl Water Sci 9:28. https://doi.org/10.1007/s13201-019-0906-z
Burow KR, Nolan BT, Rupert MG, Dubrovsky NM (2010) Nitrate in groundwater of the United States, 1991-2003. Environ Sci Technol 44:4988–4997. https://doi.org/10.1021/es100546y
Buyanjargal A (2018) Removal of nitrate and phosphate in groundwater using sequential passive treatment systems. MSc Thesis. Jeonbuk National University, Jeonju, Korea
Carlsson H, Aspegren H, Lee N, Hilmer A (1997) Calcium phosphate precipitation in biological phosphorus removal systems. Water Res 31:1047–1055. https://doi.org/10.1016/S0043-1354(96)00282-5
Carpenter SR, Caraco NF, Correll DL, Howarth RW, Sharpley AN, Smith VH (1998) Nonpoint pollution of surface waters with phosphorus and nitrogen. Ecol Appl 8:559–568. https://doi.org/10.1890/1051-0761(1998)008[0559:NPOSWW]2.0.CO;2
Chen X, Chen X, Wan X, Weng B, Huang Q (2010) Water hyacinth (Eichhornia crassipes) waste as an adsorbent for phosphorus removal from swine wastewater. Bioresour Technol 101:9025–9030. https://doi.org/10.1016/j.biortech.2010.07.013
Chintala R, Schumacher TE, McDonald LM, Clay DE, Malo DD, Papiernik SK, Clay SA, Julson JL (2014) Phosphorus sption and availability from biochars and soil/biochar mixtures. CLEAN – Soil Air Water 42:626–634. https://doi.org/10.1002/clen.201300089
Cho D-W, Song H, Schwartz FW, Kim B, Jeon B-H (2015) The role of magnetite nanoparticles in the reduction of nitrate in groundwater by zero-valent iron. Chemosphere 125:41–49. https://doi.org/10.1016/j.chemosphere.2015.01.019
De-Bashan LE, Bashan Y (2004) Recent advances in removing phosphorus from wastewater and its future use as fertilizer (1997–2003). Water Res 38:4222–4246. https://doi.org/10.1016/j.watres.2004.07.014
Driescher E, Gelbrecht J (1993) Assessing the diffuse phosphorus input from subsurface to surface waters in the catchment area of the lower River Spree (Germany). Water Sci Technol 28:337–347. https://doi.org/10.2166/wst.1993.0436
Fox S, Mozes N, Lahav O (2015) Treatment of nitrate-rich saline effluent by using citrate-rich waste as carbon source and electron donor in a single-stage activated sludge reactor. Water Air Soil Pollut 226:134–143. https://doi.org/10.1007/s11270-015-2399-1
Gandhi S, Oh B-T, Schnoor JL, Alvarez PJ (2002) Degradation of TCE, Cr (VI), sulfate, and nitrate mixtures by granular iron in flow-through columns under different microbial conditions. Water Res 36:1973–1982. https://doi.org/10.1016/S0043-1354(01)00409-2
Gao G, Xiong H, Chen J, Chen K, Chen P, Yu C, Zhu A (2018) Hydroponic method for ramie and removal of nitrogen and phosphorus from livestock wastewater. Int J Phytoremediat 20:545–551. https://doi.org/10.1080/15226514.2017.1393395
Gao Q, Wang C-Z, Liu S, Hanigan D, Liu S-T, Zhao H-Z (2019) Ultrafiltration membrane microreactor (MMR) for simultaneous removal of nitrate and phoaphte from water. Chem Eng J 355:238–246. https://doi.org/10.1016/j.cej.2018.08.137
Hekmatzadeh AA, Karimi-Jashni A, Talebbeydokhti N, Kløve B (2013) Adsorption kinetics of nitrate ions on ion exchange resin. Desalination 326:125–134. https://doi.org/10.1016/j.desal.2013.07.017
Hermassi M, Valderrama C, Dosta J, Cortina JL, Batis NH (2015) Evaluation of hydroxyapatite crystallization in a batch reactor for the valorization of alkaline phosphate concentrates from wastewater treatment plants using calcium chloride. Chem Eng J 267:142–152. https://doi.org/10.1016/j.cej.2014.12.079
Hussain SI, Blowes DW, Ptacek CJ, Olding D (2014) Phosphorus removal from lake water using basic oxygen furnace slag: System performance and characterization of reaction products. Environ Eng Sci 31:631–642. https://doi.org/10.1089/ees.2014.0074
Illeghems K, Weckx S, De Vuyst L (2015) Applying meta-pathway analyses through metagenomics to identify the functional properties of the major bacterial communities of a single spontaneous cocoa bean fermentation process sample. Food Microbiol 50:54–63. https://doi.org/10.1016/j.fm.2015.03.005
Islam M, Mishra S, Swain SK, Patel R, Dey R, Naushad M (2014) Evaluation of phosphate removal efficiency from aqueous solution by polypyrrole/BOF slag nanocomposite. Sep Sci Technol 49:2668–2680. https://doi.org/10.1080/01496395.2014.933981
Jellali S, Wahab MA, Anane M, Riahi K, Bousselmi L (2010) Phosphate mine wastes reuse for phosphorus removal from aqueous solutions under dynamic conditions. J Hazard Mater 184:226–233. https://doi.org/10.1016/j.jhazmat.2010.08.026
Kaown D, Hyun Y, Bae G-O, Lee K-K (2007) Factors affecting the spatial pattern of nitrate contamination in shallow groundwater. J Environ Qual 36:1479–1487. https://doi.org/10.2134/jeq2006.0361
Kim K-H, Yun S-T, Kim H-K, Kim J-W (2015) Determination of natural backgrounds and thresholds of nitrate in South Korean groundwater using model-based statistical approaches. J Geochem Explor 148:196–205. https://doi.org/10.1016/j.gexplo.2014.10.001
Kishida N, Tsuneda S, Kim JH, Sudo R (2009) Simultaneous nitrogen and phosphorus removal from high-strength industrial wastewater using aerobic granular sludge. J Environ Eng 135:153–158. https://doi.org/10.1061/(ASCE)0733-9372(2009)135:3(153)
Klaassen C (2007) Casarett & doull's toxicology: the basic science of poisons, seventh edn. McGraw-hill, New York
Knowles R (1982) Denitrification. Microbiol Rev 46:43–70. https://doi.org/10.1128/MMBR.46.1.43-70.1982
Kõiv M, Liira M, Mander Ü, Mõtlep R, Vohla C, Kirsimäe K (2010) Phosphorus removal using Ca-rich hydrated oil shale ash as filter material-the effect of different phosphorus loadings and wastewater compositions. Water Res 44:5232–5239. https://doi.org/10.1016/j.watres.2010.06.044
Larsdotter K, Jansen JC, Dalhammar G (2007) Biologically mediated phosphorus precipitation in wastewater treatment with microalgae. Environ Technol 28:953–960. https://doi.org/10.1080/09593332808618855
Lau P, Tam N, Wong Y (1997) Wastewater nutrients (N and P) removal by carrageenan and alginate immobilized Chlorella vulgaris. Environ Technol 18:945–951. https://doi.org/10.1080/09593331808616614
Lu SG, Bai SQ, Zhu L, Shan HD (2009) Removal mechanism of phosphate from aqueous solution by fly ash. J Hazard Mater 161:95–101. https://doi.org/10.1016/j.jhazmat.2008.02.123
Marraffa JM, Hui A, Stork CM (2004) Severe hyperphosphatemia and hypocalcemia following the rectal administration of a phosphate-containing Fleet® pediatric enema. Pediatr Emerg Care 20:453–456. https://doi.org/10.1097/01.pec.0000132217.65600.52
Martino GP, Quintana IM, Espariz M, Blancato VS, Magni C (2016) Aroma compounds generation in citrate metabolism of Enterococcus faecium: genetic characterization of type I citrate gene cluster. Int J Food Microbiol 218:27–37. https://doi.org/10.1016/j.ijfoodmicro.2015.11.004
McLay CDA, Dragten R, Sparling G, Selvarajah N (2001) Predicting groundwater nitrate concentration in a region of mixed agricultural land use: a comparison of three approaches. Environ Pollut 115:191–204. https://doi.org/10.1016/S0269-7491(01)00111-7
Meyer JL (1974) Formation constants for interaction of citrate with clacium and magnesium ions. Anal Biochem 62:295–300. https://doi.org/10.1016/0003-2697(74)90391-1
Mino T, van Loosdrecht MCM, Heijnen JJ (1998) Microbiology and biochemistry of the enhanced biological phosphate removal process. Water Res 32:3193–3207. https://doi.org/10.1016/S0043-1354(98)00129-8
Mukherjee D, Ray R, Biswas N (2020) Mining phosphate from wastewater: treatment and reuse. In: Stagner JA, Ting DSK (eds) Sustaining Resources for Tomorrow. Springer International Publishing, Cham, pp 67–81. https://doi.org/10.1007/978-3-030-27676-8_3
Muus J, Lebel H (1936) On complex calcium citrate. Mat Fys Med 19:1–17
Nancollas GH, LoRe M, Perez L, Richardson C, Zawacki SJ (1989) Mineral phases of calcium phosphate. Anat Rec 224:234–241. https://doi.org/10.1002/ar.1092240213
Palmer-Felgate EJ, Mortimer RJG, Krom MD, Jarvie HP (2010) Impact of point-source pollution on phosphorus and nitrogen cycling in stream-bed sediments. Environ Sci Technol 44:908–914. https://doi.org/10.1021/es902706r
Park J-Y, Byun H-J, Choi W-H, Kang W-H (2008) Cement paste solumn for simultaneous removal of fluoride, phosphate, and nitrate in acidic wastewater. Chemosphere 70:1429–1437. https://doi.org/10.1016/j.chemosphere.2007.09.012
Parkhurst DL, Appelo CAJ (1999) User’s guide to PHREEQC (Version 2): a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. Water-Resour Investig Rep 99:312
Penn C, Livingston S, Shedekar V, King K, Williams M (2020) Performance of field-scale phosphorus removal structures utilizing steel slag for treatment of subsurface drainage. Water 12:443. https://doi.org/10.3390/w12020443
Qian J, Wang L, Zhan H, Chen Z (2011) Urban land-use effects on groundwater phosphate distribution in a shallow aquifer, Nanfei River basin, China. Hydrol J 19:1431–1442. https://doi.org/10.1007/s10040-011-0770-x
Razzaque MS (2011) Phosphate toxicity: new insights into an old problem. Clin Sci 120:91–97. https://doi.org/10.1042/CS20100377
Recillas S, Rodríguez-Lugo V, Montero ML, Viquez-Cano S, Hernandez L, Castaño VM (2012) Studies on the precipitation behavior of calcium phosphate solutions. J Ceram Process Res 13:5–10
Robertson WD (2010) Nitrate removal rates in woodchip media of varying age. Ecol Eng 36:1581–1587. https://doi.org/10.1016/j.ecoleng.2010.01.008
Robinson C (2015) Review on groundwater as a source of nutrients to the Great Lakes and their tributaries. J Great Lakes Res 41:941–950. https://doi.org/10.1016/j.jglr.2015.08.001
Rout PR, Bhunia P, Dash RR (2017) Simultaneous removal of nitrogen and phosphorus from domestic wastewater usign Bacillus cereus GS-5 strain exhibiting heterotrophic nitrification, aerobic denitrification and denitrifying phosphorus removal. Bioresour Technol 244:484–495. https://doi.org/10.1016/j.biortech.2017.07.186
Roy JW, Bickerton G (2014) Elevated dissolved phosphorus in riparian groundwater along gaining urban streams. Environ Sci Technol 48:1492–1498. https://doi.org/10.1021/es404801y
Rubio-Rincón FJ, Lopez-Vazquez CM, Welles L, van Loosdrecht MCM, Brdjanovic D (2017) Cooperation between Candidatus competibacter and Candidatus accumulibacter clade I, in denitrification and phosphate removal processes. Water Res 120:156–164. https://doi.org/10.1016/j.watres.2017.05.001
Sengupta S, Pandit A (2011) Selective removal of phosphorus from wastewater combined with its recovery as a solid-phase fertilizer. Water Res 45:3318–3330. https://doi.org/10.1016/j.watres.2011.03.044
Shear M, Kramer B (1928) Composition of bone V. some properties of calcium citrate. J Biol Chem 79:161–175
Singh AL (2013) Nitrate and phosphate contamination in water and possible remedial measures. In: Dwivedi N (ed) Environmental Problems and Plant. Springer Verlag GmbH, Heidelberg, pp 44–56
Singh RP, Yeboah DY, Pambld ER, Dbayle P (1991) Stability constant of the calcium-citrate (3-) ion pair complex. J Chem Eng Data 36:52–54. https://doi.org/10.1021/je00001a015
Smolders AJP, Lucassen ECHET, Bobbink R, Roelofs JGM, Lamers LPM (2010) How nitrate leaching from agricultural lands provokes phosphate eutrophication in groundwater fed wetlands: the sulphur bridge. Biogeochemistry 98:1–7. https://doi.org/10.1007/s10533-009-9387-8
Song Y, Hahn HH, Hoffmann E (2002) Effects of solution conditions on the precipitation of phosphate for recovery: a thermodynamic evaluation. Chemosphere 48:1029–1034. https://doi.org/10.1016/S0045-6535(02)00183-2
Su C, Puls RW (2004) Nitrate reduction by zerovalent iron: effects of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate. Environ Sci Technol 38:2715–2720. https://doi.org/10.1021/es034650p
Su C, Puls RW (2007) Removal of added nitrate in the single, binary, and ternary systems of cotton burr compost, zerovalent iron, and sediment: implications for groundwater nitrate remediation using permeable reactive barriers. Chemosphere 67:1653–1662. https://doi.org/10.1016/j.chemosphere.2006.09.059
Szecsody J, Burns C, Moore R, Fruchter J, Vermeul V, Williams M, Girvin D, McKinley J, Truex M, Phillips J (2007) Hanford 100-N area apatite emplacement: laboratory results of ca-citrate-po4 solution injection and sr-90 immobilization in 100-n sediments, Pacific Northwest National Lab. (PNNL), Richland, Wash. https://doi.org/10.2172/936598
Tunesi S, Poggi V, Gessa C (1999) Phosphate adsorption and precipitation in calcareous soils: the role of calcium ion in solution and carbonate minerals. Nutr Cycl Agroecosyst 53:219–227. https://doi.org/10.1023/A:1009709005147
Vadas PA, Srinivasan MS, Kleinman PJA, Schmidt JP, Allen AL (2007) Hydrology and groundwater nutrient concentrations in a ditch-drained agroecosystem. J Soil Water Conserv 62:178–188
Vanek V (1993) Transport of groundwater-borne phosphorus to Lake Bysjön, South Sweden. Hydrobiologia 251:211–216. https://doi.org/10.1007/978-94-011-1602-2_23
Walker CW, Shannon RD (2006) Nitrate and phosphate removal effects of compost amendments in wetland mesocosms. T ASABE 49:1773–1778. https://doi.org/10.13031/2013.22298
Watanabe I, Furusaka C (1980) Microbial ecology of flooded rice soils. In: Alexander M (ed) Advances in Microbial Ecology. Springer US, Boston, pp 125–168. https://doi.org/10.1007/978-1-4615-8291-5_4
Xue D, Yu H, Fang Y, Shan J, Xi D, Wang Y, Kuzyakov Y, Wang Z-L, (2020) 15N-tracer approach to assess nitrogen cycling processes: Nitrate reduction, anammox and denitrification in different pH cropland soils. CATENA 193:104611. https://doi.org/10.1016/j.catena.2020.104611
Yang Z, Si S, Zeng X, Zhang C, Dai H (2008) Mechanism and kinetics of apatite formation on nanocrystalline TiO2 coatings: a quartz crystal microbalance study. Acta Biomater 4:560–568. https://doi.org/10.1016/j.actbio.2007.10.003
Yang Y, Chen T, Zhang X, Qing C, Wang J, Yue Z, Liu H, Yang Z (2018) Simultaneous removal of nitrate and phosphate from wastewater by siderite based qutotrophic denitrification. Chemosphere 199:130–137. https://doi.org/10.1016/j.chemosphere.2018.02.014
Zou H, Wang Y (2016) Phosphorus removal and recovery from domestic wastewater in a novel process of enhanced biological phosphorus removal coupled with crystallization. Bioresour Technol 211:87–92. https://doi.org/10.1016/j.biortech.2016.03.073
Zumft WG (1997) Cell biology and molecular basis of denitrification. Microbiol Mol Biol Rev 61:533–616
Availability of data and materials
Not applicable.
Funding
This research was supported by the National Research Foundation of Korea (NRF) grant funded by the Ministry of Science and ICT (NRF-2019R1A2C1086667), and by research funds of Jeonbuk National University in 2020.
Author information
Authors and Affiliations
Contributions
Jiyoung Kang: Methodology, formal analysis and investigation, and writing - original draft preparation; Sung-Wook Jeen: Conceptualization, writing - review and editing, funding acquisition, resources, and supervision
Corresponding author
Ethics declarations
Ethics approval
The authors approve the Ethical Responsibilities of Authors, as shown in the Submission Guidelines of the Journal.
Consent to participate
Not applicable.
Consent to publish
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Tito Roberto Cadaval Jr
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
ESM 1
(DOCX 806 kb)
Rights and permissions
About this article
Cite this article
Kang, J., Jeen, SW. Simultaneous removal of nitrate and phosphate in groundwater using Ca-citrate complex. Environ Sci Pollut Res 28, 35738–35750 (2021). https://doi.org/10.1007/s11356-021-13312-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-021-13312-y