Cellulose Acetate Microbeads for Controlled Delivery of Essential Micronutrients.

The controlled delivery of micronutrients to soil and plants is essential to increase agricultural yields. However, this is today achieved using fossil fuel-derived plastic carriers, posing environmental risks and contributing to global carbon emissions. In this work, a novel and efficient way to prepare biodegradable zinc-impregnated cellulose acetate beads for use as controlled release fertilizers is presented. Cellulose acetate solutions in DMSO were dropped into aqueous antisolvent solutions of different zinc salts. The droplets underwent phase inversion, forming solid cellulose acetate beads containing zinc, as a function of zinc salt type and concentration. Even higher values of zinc uptake (up to 15.5%) were obtained when zinc acetate was added to the cellulose acetate-DMSO solution, prior to dropping in aqueous zinc salt antisolvent solutions. The release profile in water of the beads prepared using the different solvents was linked to the properties of the counter-ions via the Hofmeister series. Studies in soil showed the potential for longer release times, up to 130 days for zinc sulfate beads. These results, together with the efficient bead production method, demonstrate the potential of zinc-impregnated cellulose acetate beads to replace the plastic-based controlled delivery products used today, contributing to the reduction of carbon emissions and potential environmental impacts due to the uptake of plastic in plants and animals.

Assessment of selenium spatial distribution using µ-XFR in cowpea (Vigna unguiculata (L.) Walp.) plants: Integration of physiological and biochemical responses.

Low concentrations of selenium (Se) are beneficial for plant growth. Foliar Se application at high concentrations is toxic to plants due to the formation of reactive oxygen species (ROS). This study characterized Se toxicity symptoms using X-ray fluorescence (XRF) technique in response to foliar Se application in cowpea plants. Five Se concentrations (0, 10, 25, 50, 100 e 150 g ha-1) were sprayed on leaves as sodium selenate. The visual symptoms of Se toxicity in cowpea leaves were separated into two stages: I) necrotic points with an irregular distribution and internerval chlorosis at the leaf limb border (50-100 g ha-1); II) total chlorosis with the formation of dark brown necrotic lesions (150 g ha-1). Foliar Se application at 50 g ha-1 increased photosynthetic pigments and yield. Ultrastructural analyses showed that Se foliar application above 50 g ha-1 disarranged the upper epidermis of cowpea leaves. Furthermore, Se application above 100 g ha-1 significantly increased the hydrogen peroxide concentration and lipid peroxidation inducing necrotic leaf lesions. Mapping of the elements in leaves using the XRF revealed high Se intensity, specifically in leaf necrotic lesions accompanied by calcium (Ca) as a possible attenuating mechanism of plant stress. The distribution of Se intensities in the seeds was homogeneous, without specific accumulation sites. Phosphorus (P) and sulfur (S) were found primarily located in the embryonic region. Understanding the factors involved in Se accumulation and its interaction with Ca support new preventive measurement technologies to prevent Se toxicity in plants.

Persistent Calyxes in Postbloom Fruit Drop: A Microscopy and Microanalysis Perspective.

Citrus postbloom fruit drop, caused by Colletotrichum spp., is an important disease in the Americas. The pathogen infects citrus flowers, produces orange-brown lesions on petals, and may cause the abscission of young fruit. In diseased flowers, the calyxes remain attached to the peduncle after the young fruit drop. No anatomical and microanalysis studies have been conducted to determine whether calyx tissues can be infected by Colletotrichum spp. and why calyxes remain attached to the peduncle. Based on light microscopy, we demonstrate that the ovary abscission zone exhibits a separation region composed of layers of thickened lignified walled cells, indicating that abscission involves the disruption of cell walls. The first layers of the protective zone (PZ) are composed of densely packed cells with suberized walls produced by the wound meristem. Beneath the PZ, there is a compact mass of small cells that accumulate starch grains. X-ray fluorescence microanalysis (µ-XRF) confirmed the increased accumulation of calcium in the receptacle of the persistent calyxes compared to non-inoculated citrus flowers. Moreover, the peduncle pith and the receptacle exhibit hypertrophied cells with thick walls that may be related to calyx retention. Fungal structures are not observed inside the persistent calyx tissues.

Space-resolved determination of the mineral nutrient content in tree-rings by X-ray fluorescence.

X-ray fluorescence spectroscopy (XRF) offers rapid, multi-elemental, low cost and non-destructive elemental analysis. Different studies have used this technique to investigate distribution and concentration of essential and deleterious elements in vegetation. Special emphasis has been recently placed on the key aspects concerning sampling processes, laboratory protocols and calibration methods for quantitative analysis. The aim of the present study was to develop a quantitative methodology to determine the nutrient content in Pinus taeda tree-rings by XRF. Using a 1 mm X-ray excitation beam from a Rh X-ray tube at 30 kV and 600 µA, and dwell time of 20 s, we present calibration curves for P, S, K, Ca, Mn and Fe based on multi-elemental standard addition using wood matrix of 17-year-old Pinus taeda trees. Satisfactory recoveries of our XRF approach for Ca, P, Mn, S and K (<115%), and tolerable for Fe (123%) were obtained compared to inductively coupled plasma optical emission spectrometry results. The non-destructive and quantitative XRF method allows assessing annual element concentrations of P. taeda trees, in order to provide tools for monitoring the nutrient dynamic in an experimental plantation. Furthermore, a method for elemental quantification based on multi-elemental standard addition using wood matrix is described as a useful procedure for future applications.

X-ray fluorescence spectroscopy (XRF) applied to plant science: challenges towards in vivo analysis of plants.

X-ray fluorescence spectroscopy (XRF) is an analytical tool used to determine the elemental composition in a myriad of sample matrices. Due to the XRF non-destructive feature, this technique may allow time-resolved plant tissue analyses under in vivo conditions, and additionally, the combination with other non-destructive techniques. In this study, we employed handheld and benchtop XRF to evaluate the elemental distribution changes in living plant tissues exposed to X-rays, as well as real-time uptake kinetics of Zn(aq) and Mn(aq) in soybean (Glycine max (L.) Merrill) stem and leaves, for 48 hours, combined with transpiration rate assessment on leaves by an infrared gas analyzer (IRGA). We found higher Zn content than Mn in stems. The latter micronutrient, in turn, presented higher concentration in leaf veins. Besides, both micronutrients were more concentrated in the first trifolium (i.e., youngest leaf) of soybean plants. Moreover, the transpiration rate was more influenced by circadian cycles than Zn and Mn uptake. Thus, XRF represents a convenient tool for in vivo nutritional studies in plants, and it can be coupled successfully to other analytical techniques.