Register      Login
Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH FRONT

Investigating the foliar uptake of zinc from conventional and nano-formulations: a methodological study

Thea L. Read https://orcid.org/0000-0002-5938-8201 A , Casey L. Doolette https://orcid.org/0000-0002-8092-3520 A E , Tom Cresswell https://orcid.org/0000-0002-5320-7553 B , Nicholas R. Howell https://orcid.org/0000-0003-3703-7598 B , Robert Aughterson https://orcid.org/0000-0002-1704-024X B , Inna Karatchevtseva B , Erica Donner https://orcid.org/0000-0001-6465-2233 A , Peter M. Kopittke https://orcid.org/0000-0003-4948-1880 C , Jan K. Schjoerring https://orcid.org/0000-0002-2852-3298 D and Enzo Lombi https://orcid.org/0000-0003-3384-0375 A
+ Author Affiliations
- Author Affiliations

A University of South Australia, Future Industries Institute, Mawson Lakes, SA 5095, Australia.

B Australian Nuclear Science and Technology Organisation (ANSTO), Sydney, Lucas Heights, NSW 2234, Australia.

C The University of Queensland, School of Agriculture and Food Sciences, St Lucia, Qld 4072, Australia.

D Department of Plant and Environmental Sciences, Faculty of Science, University of Copenhagen, DK-1871 Frederiksberg C, Denmark.

E Corresponding author. Email: casey.doolette@unisa.edu.au

Environmental Chemistry 16(6) 459-469 https://doi.org/10.1071/EN19019
Submitted: 18 January 2019  Accepted: 17 April 2019   Published: 6 June 2019

Environmental context. Zinc, an essential micronutrient often applied to crops as a fertiliser, can be difficult to analyse in plants due to limitations of conventional techniques. Here, we use radiotracers and a non-destructive imaging technique to visualise how zinc applied as a nanofertiliser moves within wheat plants over time. This is an important step towards developing cost-effective fertilisers to help solve one of the world’s most widespread plant deficiencies.

Abstract. Zinc (Zn) deficiency affects half of the world’s arable soil and one-third of the world’s human population. Application of Zn foliar fertilisers to cereal crops can be an effective way to increase grain Zn content; however, commonly used formulations can scorch the leaf (e.g. soluble Zn salts) or are prohibitively expensive (e.g. chelated Zn, ZnEDTA). Zinc oxide nanoparticles (ZnO-NPs) may offer an efficient and cost-effective alternative, but little is known regarding the mechanisms of Zn uptake and translocation within the plant. Foliar-applied Zn is analytically challenging to detect, locate and quantify, as it is omnipresent. Furthermore, any single analytical technique does not have the detection limit or spatial resolution required. In this study, the uptake and mobility of foliar-applied ZnEDTA, ZnO-NPs and ZnO microparticles (ZnO-MPs) to wheat (Triticum aestivum L.) were investigated using inductively coupled plasma mass spectroscopy (ICP-MS), synchrotron-based X-ray fluorescence microscopy (XFM) and radiotracing techniques using 65Zn-labelled formulations. The three techniques were compared to highlight limitations and advantages of each. We also report, for the first time, a novel time-resolved in vivo autoradiography imaging technique that can be used to visualise 65Zn in live plants treated with foliar applications of 65ZnO-NPs and MPs. The images were supplemented by gamma spectroscopy analysis for quantification. The results of this study provide important insights into the analytical challenges faced when investigating foliar-applied Zn nanofertilisers in plants. Potential solutions using nuclear techniques are also discussed, which in turn may ultimately lead to the development of more efficient foliar fertilisers.


References

Alloway BJ (2008a). Micronutrients and crop production: an introduction. In ‘Micronutrient deficiencies in global crop production’. (Ed. BJ Alloway) pp. 1–41. (Springer Science: Reading)

Alloway BJ (2008b). ‘Zinc in soils and crop nutrition, 2nd edn.’ (International Zinc Association and International Fertilizer Industry Association: Brussels and Paris)

Benoit G, Hunter KS, Rozan TF (1997). Sources of trace metal contamination artifacts during collection, handling, and analysis of freshwaters. Analytical Chemistry 69, 1006–1011.
Sources of trace metal contamination artifacts during collection, handling, and analysis of freshwatersCrossref | GoogleScholarGoogle Scholar |

Bhattacharjee S (2016). DLS and zeta potential – what they are and what they are not?. Journal of Controlled Release 235, 337–351.
DLS and zeta potential – what they are and what they are not?Crossref | GoogleScholarGoogle Scholar | 27297779PubMed |

Brennan RF (1991). Effectiveness of zinc sulfate and zinc chelate as foliar sprays in alleviating zinc deficiency of wheat grown on zinc-deficient soils in Western-Australia. Australian Journal of Experimental Agriculture 31, 831–834.
Effectiveness of zinc sulfate and zinc chelate as foliar sprays in alleviating zinc deficiency of wheat grown on zinc-deficient soils in Western-AustraliaCrossref | GoogleScholarGoogle Scholar |

Cakmak I, Kutman UB (2018). Agronomic biofortification of cereals with zinc: a review. European Journal of Soil Science 69, 172–180.
Agronomic biofortification of cereals with zinc: a reviewCrossref | GoogleScholarGoogle Scholar |

Davis RA, Rippner DA, Hausner SH, Parikh SJ, McElrone AJ, Sutcliffe JL (2017). In vivo tracking of copper-64 radiolabeled nanoparticles in Lactuca sativa. Environmental Science & Technology 51, 12537–12546.
In vivo tracking of copper-64 radiolabeled nanoparticles in Lactuca sativaCrossref | GoogleScholarGoogle Scholar |

Doolette CL, Read TL, Li C, Scheckel KG, Donner E, Kopittke PM, Schjoerring JK, Lombi E (2018). Foliar application of zinc sulphate and zinc EDTA to wheat leaves: differences in mobility, distribution, and speciation. Journal of Experimental Botany 69, 4469–4481.
Foliar application of zinc sulphate and zinc EDTA to wheat leaves: differences in mobility, distribution, and speciationCrossref | GoogleScholarGoogle Scholar | 29931117PubMed |

Du Y, Kopittke PM, Noller BN, James SA, Harris HH, Xu ZP, Li P, Mulligan DR, Huang L (2015). In situ analysis of foliar zinc absorption and short-distance movement in fresh and hydrated leaves of tomato and citrus using synchrotron-based X-ray fluorescence microscopy. Annals of Botany 115, 41–53.
In situ analysis of foliar zinc absorption and short-distance movement in fresh and hydrated leaves of tomato and citrus using synchrotron-based X-ray fluorescence microscopyCrossref | GoogleScholarGoogle Scholar | 25399024PubMed |

Dufour A, Migon C (2017). Mineralisation of atmospheric aerosol particles and further analysis of trace elements by inductively coupled plasma–optical emission spectrometry. MethodsX 4, 191–198.
Mineralisation of atmospheric aerosol particles and further analysis of trace elements by inductively coupled plasma–optical emission spectrometryCrossref | GoogleScholarGoogle Scholar | 28664147PubMed |

EAG Laboratories (2017). ICP-OES and ICP-MS detection limit guidance. Available at http://www.nanoscience.co.jp/surface_analysis/pdf/icp-oes-ms-detection-limit-guidance-BR023.pdf [Verified 11 January 2019]

Erenoglu B, Nikolic M, Römheld V, Cakmak I (2002). Uptake and transport of foliar applied zinc (65Zn) in bread and durum wheat cultivars differing in zinc efficiency. Plant and Soil 241, 251–257.
Uptake and transport of foliar applied zinc (65Zn) in bread and durum wheat cultivars differing in zinc efficiencyCrossref | GoogleScholarGoogle Scholar |

EverZinc (2017). Zinc oxide. Available at https://www.everzinc.com/zinc-oxide/ [Verified 11 January 2019]

Fowdar HS, Hatt BE, Cresswell T, Harrison JJ, Cook PLM, Deletic A (2017). Phosphorus fate and dynamics in greywater biofiltration systems. Environmental Science & Technology 51, 2280–2287.
Phosphorus fate and dynamics in greywater biofiltration systemsCrossref | GoogleScholarGoogle Scholar |

Günther D, Hattendorf B (2005). Solid sample analysis using laser ablation inductively coupled plasma mass spectrometry. TrAC Trends in Analytical Chemistry 24, 255–265.
Solid sample analysis using laser ablation inductively coupled plasma mass spectrometryCrossref | GoogleScholarGoogle Scholar |

Gupta RK, Gangoliya SS, Singh NK (2015). Reduction of phytic acid and enhancement of bioavailable micronutrients in food grains. Journal of Food Science and Technology 52, 676–684.
Reduction of phytic acid and enhancement of bioavailable micronutrients in food grainsCrossref | GoogleScholarGoogle Scholar | 25694676PubMed |

Hallmans G, Liden S (1979). Penetration of 65Zn through the skin of rats. Acta Dermato-Venereologica 59, 105–112.

Hansen TH, de Bang TC, Laursen KH, Pedas P, Husted S, Schjoerring JK (2013). Multielement plant tissue analysis using ICP spectrometry. In ‘Plant mineral nutrients. Methods in molecular biology (methods and protocols)’. (Ed. F Maathuis) pp. 121–41. (Humana Press: Totowa, NJ)

Hare DJ, New EJ, de Jonge MD, McColl G (2015). Imaging metals in biology: balancing sensitivity, selectivity and spatial resolution. Chemical Society Reviews 44, 5941–5958.
Imaging metals in biology: balancing sensitivity, selectivity and spatial resolutionCrossref | GoogleScholarGoogle Scholar | 26505053PubMed |

He X, Ma YH, Li M, Zhang P, Li YY, Zhang ZY (2013). Quantifying and imaging engineered nanomaterials in vivo: challenges and techniques. Small 9, 1482–1491.
Quantifying and imaging engineered nanomaterials in vivo: challenges and techniquesCrossref | GoogleScholarGoogle Scholar | 23027545PubMed |

Hong J, Wang L, Sun Y, Zhao L, Niu G, Tan W, Rico CM, Peralta-Videa JR, Gardea-Torresdey JL (2016). Foliar-applied nanoscale and microscale CeO2 and CuO alter cucumber (Cucumis sativus) fruit quality. The Science of the Total Environment 563–564, 904–911.
Foliar-applied nanoscale and microscale CeO2 and CuO alter cucumber (Cucumis sativus) fruit qualityCrossref | GoogleScholarGoogle Scholar | 26351199PubMed |

Jiang W, Struik PC, Lingna J, Van Keulen H, Ming Z, Stomph TJ (2007). Uptake and distribution of root-applied or foliar-applied 65Zn after flowering in aerobic rice. Annals of Applied Biology 150, 383–391.
Uptake and distribution of root-applied or foliar-applied 65Zn after flowering in aerobic riceCrossref | GoogleScholarGoogle Scholar |

King CK, Dowse MC, Simpson SL, Jolley DF (2004). An assessment of five Australian polychaetes and bivalves for use in whole-sediment toxicity tests: toxicity and accumulation of copper and zinc from water and sediment. Archives of Environmental Contamination and Toxicology 47, 314–323.
An assessment of five Australian polychaetes and bivalves for use in whole-sediment toxicity tests: toxicity and accumulation of copper and zinc from water and sedimentCrossref | GoogleScholarGoogle Scholar | 15386125PubMed |

Kopittke PM, Punshon T, Paterson DJ, Tappero RV, Wang P, Blamey FPC, van der Ent A, Lombi E (2018). Synchrotron-based X-ray fluorescence microscopy as a technique for imaging of elements in plants. Plant Physiology 178, 507–523.
Synchrotron-based X-ray fluorescence microscopy as a technique for imaging of elements in plantsCrossref | GoogleScholarGoogle Scholar | 30108140PubMed |

Kranjc E, Mazej D, Regvar M, Drobne D, Remškar M (2018). Foliar surface free energy affects platinum nanoparticle adhesion, uptake, and translocation from leaves to roots in arugula and escarole. Environmental Science. Nano 5, 520–532.
Foliar surface free energy affects platinum nanoparticle adhesion, uptake, and translocation from leaves to roots in arugula and escaroleCrossref | GoogleScholarGoogle Scholar |

Li P, Du Y, Huang L, Mitter N, Xu ZP (2016). Nanotechnology promotes the R&D of new-generation micronutrient foliar fertilizers. RSC Advances 6, 69465–69478.
Nanotechnology promotes the R&D of new-generation micronutrient foliar fertilizersCrossref | GoogleScholarGoogle Scholar |

Li C, Wang P, Lombi E, Cheng M, Tang C, Howard DL, Menzies NW, Kopittke PM (2018). Absorption of foliar-applied Zn fertilizers by trichomes in soybean and tomato. Journal of Experimental Botany 69, 2717–2729.
Absorption of foliar-applied Zn fertilizers by trichomes in soybean and tomatoCrossref | GoogleScholarGoogle Scholar | 29514247PubMed |

Limbeck A, Galler P, Bonta M, Bauer G, Nischkauer W, Vanhaecke F (2015). Recent advances in quantitative LA-ICP-MS analysis: challenges and solutions in the life sciences and environmental chemistry. Analytical and Bioanalytical Chemistry 407, 6593–6617.
Recent advances in quantitative LA-ICP-MS analysis: challenges and solutions in the life sciences and environmental chemistryCrossref | GoogleScholarGoogle Scholar | 26168964PubMed |

Lombi E, de Jonge MD, Donner E, Kopittke PM, Howard DL, Kirkham R, Ryan CG, Paterson D (2011a). Fast X-ray fluorescence microtomography of hydrated biological samples. PLoS One 6, e20626
Fast X-ray fluorescence microtomography of hydrated biological samplesCrossref | GoogleScholarGoogle Scholar | 21915334PubMed |

Lombi E, Scheckel KG, Kempson IM (2011b). In situ analysis of metal(loid)s in plants: state of the art and artefacts. Environmental and Experimental Botany 72, 3–17.
In situ analysis of metal(loid)s in plants: state of the art and artefactsCrossref | GoogleScholarGoogle Scholar |

Marsalek R (2014). Particle size and zeta potential of ZnO. APCBEE Procedia 9, 13–17.
Particle size and zeta potential of ZnOCrossref | GoogleScholarGoogle Scholar |

Mortvedt J, Gilkes R (1993). Zinc fertilizers. In ‘Zinc in soils and plants’. (Ed. AD Robson) pp. 33–42 (Springer Science + Business Media, BV: Perth, WA)

Paterson D, de Jonge MD, Howard DL, Lewis W, McKinlay J, Starritt A, Kusel M, Ryan CG, Kirkham R, Moorhead G, Siddons DP (2011). The X-ray fluorescence microscopy beamline at the Australian Synchrotron. AIP Conference Proceedings 1365, 219–222.
The X-ray fluorescence microscopy beamline at the Australian SynchrotronCrossref | GoogleScholarGoogle Scholar |

Ryan C (2000). Quantitative trace element imaging using PIXE and the nuclear microprobe. International Journal of Imaging Systems and Technology 11, 219–230.
Quantitative trace element imaging using PIXE and the nuclear microprobeCrossref | GoogleScholarGoogle Scholar |

Ryan C, Jamieson D (1993). Dynamic analysis: on-line quantitative PIXE microanalysis and its use in overlap-resolved elemental mapping. Nuclear Instruments & Methods in Physics Research. Section B, Beam Interactions with Materials and Atoms 77, 203–214.
Dynamic analysis: on-line quantitative PIXE microanalysis and its use in overlap-resolved elemental mappingCrossref | GoogleScholarGoogle Scholar |

Singh A, Shivay Y (2013). Residual effect of summer green manure crops and Zn fertilization on quality and Zn concentration of durum wheat (Triticum durum Desf.) under a Basmati rice–durum wheat cropping system. Biological Agriculture and Horticulture 29, 271–287.
Residual effect of summer green manure crops and Zn fertilization on quality and Zn concentration of durum wheat (Triticum durum Desf.) under a Basmati rice–durum wheat cropping systemCrossref | GoogleScholarGoogle Scholar |

Singh C, Friedrichs S, Levin M, Birkedal R, Jensen K, Pojana G, Wohlleben W, Schulte S, Wiench K, Turney T, Koulaeva O, Marshall D, Hund-Rinke K, Kördel W, Van Doren E, De Temmerman P-J, Abi Daoud Francisco M, Mast J, Gibson N, Koeber R, Linsinger T, Klein CL (2011). NM-series of representative manufactured nanomaterials. Zinc oxide characterisation and test item preparation. (European Commission Joint Research Centre, Institute for Reference Materials and Measurements: Luxembourg)

Sonic Essentials (2019). IcON. Available at http://www.sonicessentials.com/index.php/products/icon [Verified 11 January 2019]

Sugita R, Kobayashi NI, Hirose A, Ohmae Y, Tanoi K, Nakanishi TM (2013). Non-destructive real-time radioisotope imaging system for visualizing 14C-labeled chemicals supplied as CO2 in plants using Arabidopsis thaliana. Journal of Radioanalytical and Nuclear Chemistry 298, 1411–1416.
Non-destructive real-time radioisotope imaging system for visualizing 14C-labeled chemicals supplied as CO2 in plants using Arabidopsis thalianaCrossref | GoogleScholarGoogle Scholar |

Sugita R, Kobayashi N, Hirose A, Tanoi K, Nakanishi T (2014). Evaluation of in vivo detection properties of Na-22, Zn-65, Rb-86, Cd-109 and Cs-137 in plant tissues using real-time radioisotope imaging system. Physics in Medicine and Biology 59, 837–851.
Evaluation of in vivo detection properties of Na-22, Zn-65, Rb-86, Cd-109 and Cs-137 in plant tissues using real-time radioisotope imaging systemCrossref | GoogleScholarGoogle Scholar | 24487508PubMed |

United States Environmental Protection Agency (2007). Method 3051a: microwave-assisted acid digestion of sediments, sludges, soils, and oils. Available at https://www.epa.gov/sites/production/files/2015-12/documents/3051a.pdf [verified 7 May 2019]

United States Environmental Protection Agency (2017). Clean Water Act analytical methods: method detection limit – frequent questions. Available at https://www.epa.gov/cwa-methods/method-detection-limit-frequent-questions [verified 7 May 2019]

Vert M, Doi Y, Hess K-H, Hodge P, Kubisa P, Rinaudo M, Schué F (2012). Terminology for biorelated polymers and applications (IUPAC recommendations). Pure and Applied Chemistry 84, 377–410.
Terminology for biorelated polymers and applications (IUPAC recommendations)Crossref | GoogleScholarGoogle Scholar |

Wang P, Lombi E, Sun S, Scheckel KG, Malysheva A, McKenna BA, Menzies NW, Zhao F-J, Kopittke PM (2017). Characterizing the uptake, accumulation and toxicity of silver sulfide nanoparticles in plants. Environmental Science. Nano 4, 448–460.
Characterizing the uptake, accumulation and toxicity of silver sulfide nanoparticles in plantsCrossref | GoogleScholarGoogle Scholar |

Wolf RE (2005). What is ICP-MS? ...and more importantly, what can it do? US Geological Survey Crustal Geophysics and Geochemistry Science Center. Available at https://crustal.usgs.gov/laboratories/icpms/intro.html [verified 7 May 2019]

Zadoks JC, Chang TT, Konzak CF (1974). A decimal code for the growth-stages of cereals. Weed Research 14, 415–421.
A decimal code for the growth-stages of cerealsCrossref | GoogleScholarGoogle Scholar |