Abstract
Elevated concentrations of nitrate (NO3−) and nitrite (NO2−) are possibly the most widespread contaminant in groundwater, contributing to eutrophication. However, it is also a potential nutrient which can be recovered. The present work evaluates and optimizes the removal efficiency of NO3− and NO2 using acid-modified waste coffee grounds biochar (ACGB) in aqueous solution. Central composite design (CCD) was adopted to optimize the independent variables (acid molarity, heating temperature, and storage time) influencing the removal of NO3− and NO2−. The ANOVA analysis of the CCD suggested all the independent operating parameters had significant (p value < 0.05) impacts in the removal efficiency of NO3− and NO2− by the ACGB. The results exhibited optimal removal efficiencies of 83.8% and 73.3% for NO3− and NO2−, respectively, using the modification conditions of 0.8 M HCl, at 150 °C for 60 min. This work highlights removal of NO3− and NO2− onto an organic chemical free adsorbent. Point zero charge of ACGB presumes that electrostatic attraction of the positively charged surface of ACGB has mainly contributed to removal process via adsorption. However, adjustment of pH to alkaline condition negatively impacts the removal efficiencies of NO3− and NO2− which decreased to less than 50%. The spent nitrogen enriched, ACGB has high potential to be converted into soil fertilizer.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13762-023-05182-3/MediaObjects/13762_2023_5182_Fig1_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13762-023-05182-3/MediaObjects/13762_2023_5182_Fig2_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13762-023-05182-3/MediaObjects/13762_2023_5182_Fig3_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13762-023-05182-3/MediaObjects/13762_2023_5182_Fig4_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13762-023-05182-3/MediaObjects/13762_2023_5182_Fig5_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13762-023-05182-3/MediaObjects/13762_2023_5182_Fig6_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13762-023-05182-3/MediaObjects/13762_2023_5182_Fig7_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13762-023-05182-3/MediaObjects/13762_2023_5182_Fig8_HTML.png)
Similar content being viewed by others
Data availability
All the data generated or analysed during this study are included in this article.
References
Adauto A, Sun-Kou MR (2021) Comparative study of anion removal using adsorbents prepared from a homoionic clay. Environ Nanotechnol Monit Manag 15:100476. https://doi.org/10.1016/j.enmm.2021.100476
Ahmadi Barshahi P, Hasani Zonoozi M, Saeedi M (2023) Rifampin removal using electrocoagulation: optimizing the process and improving the floated sludge dewaterability. Int J Environ Sci Technol 20:6275–6290. https://doi.org/10.1007/s13762-023-04898-6
Al-Maliky EA, Gzar HA, Al-Azawy MG (2021) Determination of point of zero charge (PZC) of concrete particles adsorbents. IOP Conf Ser Mater Sci Eng 1184:012004. https://doi.org/10.1088/1757-899X/1184/1/012004
Ariffin FD, Halim AA, Hanafiah MM et al (2019) The effects of African catfish Clarias, gariepinus pond farm’s effluent on water quality of Kesang river in Malacca, Malaysia. Appl Ecol Environ Res 17:1531–1545. https://doi.org/10.15666/aeer/1702_15311545
Ballesteros LF, Teixeira JA, Mussatto SI (2014) Chemical, functional, and structural properties of spent coffee grounds and coffee Silverskin. Food Bioprocess Technol 7:3493–3503. https://doi.org/10.1007/s11947-014-1349-z
Banu HT, Karthikeyan P, Meenakshi S (2019) Zr4+ ions embedded chitosan-soya bean husk activated bio-char composite beads for the recovery of nitrate and phosphate ions from aqueous solution. Int J Biol Macromol 130:573–583. https://doi.org/10.1016/j.ijbiomac.2019.02.100
Bayuo J, Abukari MA, Pelig-Ba KB (2020) Optimization using central composite design (CCD) of response surface methodology (RSM) for biosorption of hexavalent chromium from aqueous media. Appl Water Sci 10:135. https://doi.org/10.1007/s13201-020-01213-3
Berberich J, Li T, Sahle-Demessie E (2019) Biosensors for monitoring water pollutants: a case study with arsenic in groundwater. Separation science and technology (New York). Academic Press, pp 285–328
Bhatnagar A, Sillanpää M (2011) A review of emerging adsorbents for nitrate removal from water. Chem Eng J 168:493–504. https://doi.org/10.1016/j.cej.2011.01.103
Bryan NS, Alexander DD, Coughlin JR et al (2012) Ingested nitrate and nitrite and stomach cancer risk: an updated review. Food Chem Toxicol 50:3646–3665. https://doi.org/10.1016/j.fct.2012.07.062
Gai X, Wang H, Liu J et al (2014) Effects of feedstock and pyrolysis temperature on biochar adsorption of ammonium and nitrate. PLoS ONE 9:e113888. https://doi.org/10.1371/journal.pone.0113888
Han E-Y, Kim B-K, Kim H-B et al (2021) Reduction of nitrate using biochar synthesized by Co-Pyrolyzing sawdust and iron oxide. Environ Pollut 290:118028. https://doi.org/10.1016/j.envpol.2021.118028
Hu Q, Chen N, Feng C, Hu WW (2015) Nitrate adsorption from aqueous solution using granular chitosan-Fe3+ complex. Appl Surf Sci 347:1–9. https://doi.org/10.1016/J.APSUSC.2015.04.049
Iberahim N, Sethupathi S, Bashir MJK et al (2022) Evaluation of oil palm fiber biochar and activated biochar for sulphur dioxide adsorption. Sci Total Environ 805:150421. https://doi.org/10.1016/j.scitotenv.2021.150421
Kaczerewska O, Martins R, Figueiredo J et al (2020) Environmental behaviour and ecotoxicity of cationic surfactants towards marine organisms. J Hazard Mater 392:122299. https://doi.org/10.1016/j.jhazmat.2020.122299
Kosmulski M (2020) The pH dependent surface charging and points of zero charge. VIII. Update. Adv Colloid Interface Sci 275:102064. https://doi.org/10.1016/j.cis.2019.102064
Kumar PS, Korving L, van Loosdrecht MCM, Witkamp G-J (2019) Adsorption as a technology to achieve ultra-low concentrations of phosphate: Research gaps and economic analysis. Water Res X. 4:100029. https://doi.org/10.1016/j.wroa.2019.100029
Kyzas G (2012) A decolorization technique with spent “greek coffee” grounds as zero-cost adsorbents for industrial textile wastewaters. Materials (basel) 5:2069–2087. https://doi.org/10.3390/ma5112069
Leong K-Y, See S, Lim J-W et al (2017) Effect of process variables interaction on simultaneous adsorption of phenol and 4-chlorophenol: statistical modeling and optimization using RSM. Appl Water Sci 7:2009–2020. https://doi.org/10.1007/s13201-016-0381-8
Lim ZK, Liu T, Zheng M et al (2021) Versatility of nitrite/nitrate-dependent anaerobic methane oxidation (n-DAMO): First demonstration with real wastewater. Water Res 194:116912. https://doi.org/10.1016/j.watres.2021.116912
Lin S-S, Shen S-L, Zhou A, Xu Y-S (2020) Approach based on TOPSIS and Monte Carlo simulation methods to evaluate lake eutrophication levels. Water Res 187:116437. https://doi.org/10.1016/j.watres.2020.116437
Liu J, Cheng X, Zhang Y et al (2017) Zeolite modification for adsorptive removal of nitrite from aqueous solutions. Microporous Mesoporous Mater 252:179–187. https://doi.org/10.1016/j.micromeso.2017.06.029
Liu L, Ji M, Wang F (2018) Adsorption of Nitrate onto ZnCl2: modified coconut granular activated carbon: kinetics, characteristics, and adsorption dynamics. Adv Mater Sci Eng 2018:1–12. https://doi.org/10.1155/2018/1939032
Loganathan P, Vigneswaran S, Kandasamy J (2013) Enhanced removal of nitrate from water using surface modification of adsorbents: a review. J Environ Manage 131:363–374. https://doi.org/10.1016/j.jenvman.2013.09.034
Long L, Xue Y, Hu X, Zhu Y (2019) Study on the influence of surface potential on the nitrate adsorption capacity of metal modified biochar. Environ Sci Pollut Res 26:3065–3074. https://doi.org/10.1007/s11356-018-3815-z
Maulina S, Iriansyah M (2018) Characteristics of activated carbon resulted from pyrolysis of the oil palm fronds powder. IOP Conf Ser Mater Sci Eng. 309:012072. https://doi.org/10.1088/1757-899X/309/1/012072
Mazarji M, Aminzadeh B, Baghdadi M, Bhatnagar A (2017) Removal of nitrate from aqueous solution using modified granular activated carbon. J Mol Liq 233:139–148. https://doi.org/10.1016/j.molliq.2017.03.004
Namane A, Mekarzia A, Benrachedi K et al (2005) Determination of the adsorption capacity of activated carbon made from coffee grounds by chemical activation with ZnCl2 and H3PO4. J Hazard Mater 119:189–194. https://doi.org/10.1016/J.JHAZMAT.2004.12.006
Namsaraev Z, Melnikova A, Komova A et al (2020) Algal bloom occurrence and effects in Russia. Water 12:285. https://doi.org/10.3390/w12010285
Nandiyanto ABD, Oktiani R, Ragadhita R (2019) How to Read and Interpret FTIR Spectroscope of Organic Material. Indones J Sci Technol 4:97. https://doi.org/10.17509/ijost.v4i1.15806
Nguyen V-T, Vo T-D-H, Tran T et al (2021) Biochar derived from the spent coffee ground for ammonium adsorption from aqueous solution. Case Stud Chem Environ Eng. 4:100141. https://doi.org/10.1016/j.cscee.2021.100141
Ogata F, Tominaga H, Kangawa M et al (2012) Adsorption of nitrate, nitrite, and fluoride ions by carbonaceous material produced from coffee grounds in a complex solution system. e-J Sci Nanotechnol. https://doi.org/10.1380/ejssnt.2012.493
Ogata F, Imai D, Kawasaki N (2015) Adsorption of nitrate and nitrite ions onto carbonaceous material produced from soybean in a binary solution system. J Environ Chem Eng 3:155–161. https://doi.org/10.1016/j.jece.2014.11.025
Pashaei H, Ghaemi A, Nasiri M, Karami B (2020) Experimental modeling and optimization of CO2 absorption into piperazine solutions using RSM-CCD methodology. ACS Omega 5:8432–8448. https://doi.org/10.1021/acsomega.9b03363
Pavlović MD, Buntić AV, Mihajlovski KR et al (2014) Rapid cationic dye adsorption on polyphenol-extracted coffee grounds—A response surface methodology approach. J Taiwan Inst Chem Eng 45:1691–1699. https://doi.org/10.1016/j.jtice.2013.12.018
Peiris C, Nayanathara O, Navarathna CM et al (2019) The influence of three acid modifications on the physicochemical characteristics of tea-waste biochar pyrolyzed at different temperatures: a comparative study. RSC Adv 9:17612–17622. https://doi.org/10.1039/C9RA02729G
Premarathna KSD, Rajapaksha AU, Sarkar B et al (2019) Biochar-based engineered composites for sorptive decontamination of water: a review. Chem Eng J 372:536–550. https://doi.org/10.1016/j.cej.2019.04.097
Reffas A, Bernardet V, David B et al (2010) Carbons prepared from coffee grounds by H3PO4 activation: characterization and adsorption of methylene blue and Nylosan Red N-2RBL. J Hazard Mater 175:779–788. https://doi.org/10.1016/j.jhazmat.2009.10.076
Sengupta S, Nawaz T, Beaudry J (2015) Nitrogen and phosphorus recovery from wastewater. Curr Pollut Reports 1:155–166. https://doi.org/10.1007/s40726-015-0013-1
Singh S, Wasewar KL, Kansal SK (2020) Low-cost adsorbents for removal of inorganic impurities from wastewater. Inorganic pollutants in water. Elsevier, pp 173–203
Soundararajan R, Ramesh A, Mohanraj N, Parthasarathi N (2016) An investigation of material removal rate and surface roughness of squeeze casted A413 alloy on WEDM by multi response optimization using RSM. J Alloys Compd 685:533–545. https://doi.org/10.1016/j.jallcom.2016.05.292
Stylianou M, Christou A, Dalias P et al (2020) Physicochemical and structural characterization of biochar derived from the pyrolysis of biosolids, cattle manure and spent coffee grounds. J Energy Inst 93:2063–2073. https://doi.org/10.1016/j.joei.2020.05.002
Tan SY, Sethupathi S, Leong KH, Ahmad T (2022) Mechanism and kinetics of low concentration total phosphorus and reactive phosphate recovery from aquaculture wastewater via calcined eggshells. Water Air Soil Pollut. https://doi.org/10.1007/s11270-022-05905-1
Usman ARA, Ahmad M, El-Mahrouky M et al (2016) Chemically modified biochar produced from conocarpus waste increases NO3 removal from aqueous solutions. Environ Geochem Health 38:511–521. https://doi.org/10.1007/s10653-015-9736-6
Wang J, Wang S (2019) Preparation, modification and environmental application of biochar: a review. J Clean Prod 227:1002–1022. https://doi.org/10.1016/j.jclepro.2019.04.282
**a F, Yang H, Li L et al (2020) Enhanced nitrate adsorption by using cetyltrimethylammonium chloride pre-loaded activated carbon. Environ Technol 41:3562–3572. https://doi.org/10.1080/09593330.2019.1615133
Yin Q, Zhang B, Wang R, Zhao Z (2017) Biochar as an adsorbent for inorganic nitrogen and phosphorus removal from water: a review. Environ Sci Pollut Res 24:26297–26309. https://doi.org/10.1007/s11356-017-0338-y
Zhang M, Song G, Gelardi DL et al (2020) Evaluating biochar and its modifications for the removal of ammonium, nitrate, and phosphate in water. Water Res 186:116303. https://doi.org/10.1016/j.watres.2020.116303
Zhang Z, Huang G, Zhang P et al (2023) Development of iron-based biochar for enhancing nitrate adsorption: Effects of specific surface area, electrostatic force, and functional groups. Sci Total Environ 856:159037. https://doi.org/10.1016/j.scitotenv.2022.159037
Acknowledgements
The authors would like to thank the financial support received from Long Term Research Grant Scheme (LRGS/1/2018/USM/01/1/2) (UTAR4411/S01) under the Ministry of Higher Education Malaysia.
Author information
Authors and Affiliations
Contributions
All authors contributed to the study’s conception and design. Material preparation, data collection, analysis, and drafting of the manuscript were performed by Tan Sin Ying. Sumathi Sethupathi was involved in the project supervision and writing process: review and editing. Leong Kah Hon was involved in data curation and writing, review and editing of the manuscript. Tanveer Ahmad edited previous versions of the manuscript. All authors read and approved the final manuscript.
Corresponding author
Ethics declarations
Conflict of interest
The authors declare there is no conflict of interest regarding the publication of this article.
Ethical approval
Not applicable.
Consent to participate
Not applicable.
Consent for publication
Not applicable.
Additional information
Editorial responsibility: Ales Hanc.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Tan, SY., Sethupathi, S., Leong, KH. et al. Acid-modified coffee grounds biochar for nitrate and nitrite removal: an optimization via central composite design. Int. J. Environ. Sci. Technol. 21, 3221–3234 (2024). https://doi.org/10.1007/s13762-023-05182-3
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13762-023-05182-3