Demetrio Gonzalez

Comparative effect of ZnO NPs, ZnO bulk and ZnSO4 in the antioxidant defences of two plant species growing in two agricultural soils under greenhouse conditions

The present study has investigated the toxicity of ZnO NPs to bean (Phaseolus vulgaris) and tomato (Solanum lycopersicon) crops grown to maturity under greenhouse conditions using an acidic (soil pH5.4) and a calcareous soil (soil pH8.3). The potentially available Zn in the soils and the Zn accumulation in the leaves from NPs applied to the soil (3, 20 and 225mgZnkg-1) and changes in the chlorophylls, carotenoids and oxidative stress biomarkers were measured at 15, 30, 60 and 90days and compared with those caused by bulk ZnO and ZnSO4. The available Zn in the soil and the leaf Zn content did not differ among the Zn chemical species, except in the acidic soil at the highest concentration of Zn applied as Zn ions, where the highest values of the two variables were found. The ZnO NPs showed comparable Zn toxicity or biostimulation to their bulk counterparts and Zn salts, irrespective of certain significant differences suggesting a higher activity of the Zn ion. The treatments altered the photosynthetic pigment concentration and induced oxidative stress in plants. ROS formation was observed at Zn plant concentrations ranging from 590 to 760mgkg-1, but the effects on the rest of the parameters were highly dependent on the plant species, exposure time and especially soil type. In general, the effects were higher in the acidic soil than in the calcareous soil for the bean and the opposite for the tomato. The similar uptakes and toxicities of the different Zn forms suggest that the Zn ions derived from the ZnO NPs exerted a preferential toxicity in plants. However, several results obtained in soils treated with NPs at 3mgZnkg-1 soil indicated that may exist other underlying mechanisms related to the intrinsic nanoparticle properties, especially at low NP concentrations.

Effect of inorganic and organic copper fertilizers on copper nutrition in Spinacia oleracea and on labile copper in soil.

To ensure an optimal concentration of Cu in food crops, the effectiveness of eight liquid Cu fertilizers was studied in a spinach ( Spinacia oleracea L.) crop grown on Cu-deficient soil under greenhouse conditions. Plant dry matter yields, Cu concentrations in spinach plants (total and morpholino acid (MES)- and ethylenediaminedisuccinic acid (EDDS)-extractable), and Cu uptakes were studied. The behavior of Cu in soil was evaluated by both single and sequential extraction procedures. The highest quantities of Cu in labile forms in the soil, total uptakes, and Cu concentrations in the plants were associated with the application of the two sources that contained Cu chelated by EDTA and/or DTPA. The fertilizers containing these Cu chelates represent a promising approach to achieve high levels of agronomic biofortification. The stronger correlations obtained between low-molecular-weight organic acid-extractable Cu in soil and the Cu concentrations and Cu uptakes by the plants show the suitability of this soil extraction method for predicting Cu available to spinach plants.

Effects of aged ZnO NPs and soil type on Zn availability, accumulation and toxicity to pea and beet in a greenhouse experiment

Most studies have assessed the toxicity of pristine NPs to plants without considering the likely changes that these NPs will undergo during their residence time in the soil. In this study, we assessed the effects of ZnO NPs (3, 20, and 225 mg Zn kg-1 soil) aged for a year in soil and after a previous crop on the Zn availability in soil, leaf accumulation and toxicity to green pea (Pisum sativum L.) and beet root (Beta vulgaris L). The effects were compared to bulk ZnO and ZnSO4 in two agricultural soils with different pH under greenhouse conditions. The Zn concentration in the plant leaf was 6-12-fold higher in acidic than in calcareous soil that could explain the different effects on plants caused by Zn applications depending on soil type. Thus, in acidic soil, ZnO NPs promoted ROS generation in both plant species with increases from 47% to 130%, increased the MDA content in pea up to 58 ± 8% in plant exposed to ZnSO4 at 225 mg Zn kg-1 soil and altered the ratio of photosynthetic pigments in beet between 12% and 41%, suggesting distressed chloroplast constituents. In calcareous soil, the changes seemed to be related to the supply of Zn in Zn deficient soils, whose principal effect was the 20-65% decrease of ROS levels in treated plants. The available and leaf Zn concentrations did not differ among Zn sources. Likewise, ZnO NPs showed comparable toxic or stimulatory effects to ZnO bulk and Zn salt, with some exceptions where Zn ion showed the highest phytotoxicity and effectiveness as a micronutrient. According to our results, we cannot affirm that NPs pose a higher potential environmental risk than their bulk counterparts after one-year of residence time in soil.

The influence of moisture on the residual effects of natural zinc chelates applied to two different soils

The aim of this study was to compare the behavior of residual Zn from three natural chelates (Zn-aminolignosulfonate (Zn-AML),Zn-polyhydroxyphenylcarboxylate (Zn-PHP) and Zn-ethylenediamine disuccinate (Zn-EDDS)) applied at different rates (0, 5 and 10 mg Zn/kg soil) to a flax crop grown during the previous year. This incubation experiment was carried out over 75 days under two different moisture conditions (60% field capacity and waterlogged) in two different soils (acidic (Soil acid )and calcareous (Soil calc )). The potential available Zn concentration and short- term available Zn were estimated under both moisture conditions using the diethylenetriaminepentaacetic acid - triethanolamine (DTPA-TEA) and low-molecular-weight organic acids (LMWOAs) methods, respectively. Water- soluble Zn was estimated in both soils under 60% field capacity conditions. Immediately available Zn (the Zn concentration in the soil solution) was estimated under waterlogged conditions. The pH and Eh were also determined in both soils. Incubation of both soils under both moisture conditions led to decreases in the potential available Zn and short-term available Zn concentrations. Water-soluble Zn concentrations in soils under 60% field conditions, immediately available Zn in soils and the Eh parameter under waterlogged conditions also decreased with time. The residual effect of Zn-AML applied at a rate of 10 mg Zn/kg in Soil acid produced the highest available and short-term Zn concentrations, and the residual effect of Zn-EDDS produced the highest short-term Zn concentration in Soil calc .

Mobility in soil and availability to triticale plants of copper fertilisers

The mobility and availability to plants of copper (Cu) applied through inorganic and organic fertilisers can be important for crop production and also in terms of its environmental impact. Column and greenhouse experiments were conducted on a Typic Xerorthent soil (pH 7.09, sandy clay loam texture with moderate permeability) to study the relative migration and extractability of Cu sources in a reconstructed soil profile and the response of a triticale crop (X Triticosecale Wittmack) to the Cu supplied. The soil Cu status and quantity of Cu in the leachates were established in the soil columns according to layer depth and experimental time. Most of the Cu applied though natural (Cu-lignosulfonate, Cu-gluconate, Cu-galacturonatemonogluconate, Cu-bis(ethoxydihydroxydiethylamino)sulfate) and inorganic (Cu-oxychloride) fertilisers remained in the top soil and Cu-HEDTA migrated to a soil depth of 20 cm. Only when Cu was applied as Cu-EDTA and Cu-DTPA-HEDTA-EDTA did a large percentage of Cu remain in the top soil, initially in the water soluble fraction. The Cu associated with this fraction migrated and became distributed throughout the soil column, producing significant Cu losses due to leaching. For a 2.120 pore volume of collected leachate and an experimental time of 200 days, the leaching rates were respectively 23% and 51% of the total amount of Cu applied. The high potential availability of Cu to plants from these two sources, and to a lesser extent for Cu-lignosulfonate (applied at 2 and 3 mg Cu kg–1 rate), were correlated with the higher concentrations and uptakes of Cu by triticale grain. The advantage of this last source is that it does not produce losses due to leaching.

Influence of Moisture Conditions on Residual Zn Concentrations Applied as Synthetic Chelates

The aim of this study was to compare the behavior of residual zinc (Zn) from different synthetic chelates containing the chelating agents EDTA (ethylenediaminetetraacetate acid), HEDTA (hydroxyethyl-ethylenediaminetriacetate acid), and DTPA (diethylenetriaminepentaacetate acid) applied at different rates. This incubation experiment was carried out under two different moisture conditions (60 percent field capacity and waterlogged) and in two different soils from the central region of Spain (Soilacid, Typic Haploxeralf, and Soilcalc, Typic Calcixerept). The potentially available Zn concentration and short-term available Zn were estimated using the DTPA-TEA (diethylenetriaminepentaacetic acid–triethanolamine) and LMWOAs (low-molecular-weight organic acids) methods. In both soils, the amount of water-soluble Zn was estimated under 60 percent field-capacity conditions. Immediately available Zn was estimated under waterlogged conditions. The Zn concentrations depended on the soil type, the experimental time, and the Zn chelate used. Under both moisture conditions, the soil characteristics caused the residual effects of Zn-EDTA in Soilacid and Zn-DTPA-HEDTA-EDTA applied to Soilcalc, to produce the greatest Zn concentrations.

Comparative study of the phytotoxicity of ZnO nanoparticles and Zn accumulation in nine crops grown in a calcareous soil and an acidic soil

The increasing use of zinc oxide nanoparticles (ZnO NPs) in agriculture and consumer products has created the need to evaluate their impact on crops. Nine crops were investigated: wheat, maize, radish, bean, lettuce, tomato, pea, cucumber, and beet. The toxic effects of ZnO NPs on seed germination, plant growth, and biochemical parameters, including photosynthetic pigments, protein and malondialdehyde (MDA) content, reactive oxygen species (ROS), enzymes of the antioxidant defence system, as well as the Zn translocation in the plants were investigated using pots containing non-contaminated or ZnO NP-contaminated soil at concentrations of 20, 225, 450, and 900 mg Zn kg-1. Two soils with different physicochemical properties, namely a calcareous soil and an acidic soil, were used. The total and available Zn in the soils were correlated with the Zn in the plants (roots and shoots) and the observed effects. In the calcareous soil, the available Zn was very low and the phytotoxicity was limited to a slight reduction in the biomass for wheat, cucumber, and beet at the highest concentration. Only beet showed an increase in photosynthetic pigments. The parameters related to oxidative stress were affected to different degrees depending on the crop, with the exceptions of maize, lettuce, pea, and beet. In the acidic soil, the available Zn was high, and the germination of bean, tomato, lettuce, and beet, and the growth of most of the crops were seriously affected. The calculated EC50 values (growth) in the acidic soil ranged from 110 to 520 mg Zn kg-1. The photosynthetic pigments and most of the markers of oxidative stress were negatively affected in maize, wheat, bean, and pea. However, these changes were not always associated with a decrease in plant weight. In summary, soil pH and plant species are key factors affecting the Zn availability and phytotoxicity of ZnO NPs.