Nanoscale Zero-Valent Iron Has Minimum Toxicological Risk on the Germination and Early Growth of Two Grass Species with Potential for Phytostabilization.

Two Poaceae species, Agrostis capillaris and Festuca rubra, were selected for their potential as phytostabilizing plants in multicontaminated soils. These species are resistant to contamination and maintain high concentrations of contaminants at the root level. Nanoscale zero-valent iron (nZVI) is an engineered nanomaterial with the ability to stabilize metal(loid)s in soils; its potential toxicological effects in the selected species were studied in a germination test using: (i) control variant without soil; (ii) soil contaminated with Pb and Zn; and (iii) contaminated soil amended with 1% nZVI, as well as in an hydroponic experiment with the addition of nZVI 0, 25, 50 and 100 mg L-1. nZVI had no negative effects on seed germination or seedling growth, but was associated with an increase in shoot growth and reduction of the elongation inhibition rate (root-dependent) of F. rubra seedlings. However, applications of nZVI in the hydroponic solution had no effects on F. rubra but A. capillaris developed longer roots and more biomass. Increasing nZVI concentrations in the growing solution increased Mg and Fe uptake and reduced the Fe translocation factor. Our results indicate that nZVI has few toxic effects on the studied species.

Interactions of two novel stabilizing amendments with sunflower plants grown in a contaminated soil.

Several efficient stabilizing amendments have been recently proposed for the remediation of metal(loid)-contaminated soils. However, information on their interactions with plants, which is a crucial factor in soil environments, are still scarce. An amorphous manganese oxide (AMO) synthesized from organic compounds and nano zerovalent iron (nZVI) have been previously tested as promising stabilizing agents usable both for the stabilization of metals and As. Experiments with rhizoboxes were performed in order to evaluate their influence on the mobility of metal(loid)s in the bulk soil and rhizosphere of sunflower (Helianthus annuus L.) together with their impact on metal uptake and biomass yield. Generally, AMO proved more efficient than nZVI in all stages of experiment. Furthermore, the AMO effectively reduced water- and 0.01 M CaCl2-extractable fractions of Cd, Pb and Zn. The decreased bioavailability of contaminating metal(loid)s resulted in significant increase of microbial activity in AMO-amended soil. Together with metal(loid) extractability, the AMO was also able to significantly reduce the uptake of metals and ameliorate plant growth, especially in the case of Zn, since this metal was taken up in excessive amounts from the control soil causing strong phytotoxicity and even death of young seedlings. On the other hand, AMO application lead to significant release of Mn that was readily taken up by plants. Resulting Mn concentrations in biomass exceeded toxicity thresholds while plants were showing emergent Mn phytotoxicity symptoms. We highlight the need of such complex studies involving plants and soil biota when evaluating the efficiency of stabilizing amendments in contaminated soils.

Exposure of engineered nanomaterials to plants: Insights into the physiological and biochemical responses-A review.

Recent investigations show that carbon-based and metal-based engineered nanomaterials (ENMs), components of consumer goods and agricultural products, have the potential to build up in sediments and biosolid-amended agricultural soils. In addition, reports indicate that both carbon-based and metal-based ENMs affect plants differently at the physiological, biochemical, nutritional, and genetic levels. The toxicity threshold is species-dependent and responses to ENMs are driven by a series of factors including the nanomaterial characteristics and environmental conditions. Effects on the growth, physiological and biochemical traits, production and food quality, among others, have been reported. However, a complete understanding of the dynamics of interactions between plants and ENMs is not clear enough yet. This review presents recent publications on the physiological and biochemical effects that commercial carbon-based and metal-based ENMs have in terrestrial plants. This document focuses on crop plants because of their relevance in human nutrition and health. We have summarized the mechanisms of interaction between plants and ENMs as well as identified gaps in knowledge for future investigations.

Maghemite nanoparticles and ferrous sulfate for the stimulation of iron plaque formation and arsenic immobilization in Phragmites australis.

Wetland plants are considered as suitable biofilters for the removal of metal(loid)s and other contaminants from waters and wastewaters, due to their ability to accumulate and retain the contaminants in their roots. The iron plaque (IP) on the root surface influences the metal(loid)s retention processes. The stimulation of the IP development on roots of Phragmites australis by the external supply of a novel synthetic nanomaterial (nanomaghemite, nFe2O3) and FeSO4 (alone or in combination) was studied. An hydroponic experiment was carried out to evaluate the iron plaque formation after external iron addition, as well as their influence on arsenic immobilization capacity. Microscopic and spectroscopic techniques were utilized to assess the distribution of Fe and As in the roots. The addition of Fe stimulated the generation of the IP, especially when FeSO4 was involved. The nanoparticles alone were not efficient with regard to IP formation or As adsorption, even though they adhered to the root surface and did not enter into epithelial root cells. The combination of FeSO4 and nFe2O3 was the most effective treatment for improving the As removal capacity, and it seems to be an effective way to enhance the rhizofiltration potential of P. australis in As contaminated (waste)waters.

Root water transport of Helianthus annuus L. under iron oxide nanoparticle exposure.

The application of nanomaterials in commercially available products is increasing rapidly for agriculture, phytoremediation and biotechnology. Since plants suppose the first sink for the accumulation of nanoparticles from the environment, emerging studies have focused on the general consequences for plants and their effects on the biomass production. However, effects on the root surface, as well as blockage of nutrients and water uptake by the roots, may also occur. This experiment was designed to prove if the plant water relations can be affected by the adsorption of nanoparticles on the root surface, causing a consequent stress for the plants. With this goal, plants of Helianthus annuus were previously grown in a hydroponic culture, and at age of 55 days, their roots were exposed to three different concentrations of nanomaghemite (NM) in the hydroponic solution for 5 days: control without NM; 50 and 100 mg l(-1) NM. The main effect was related to the reduction of the root hydraulic conductivity (Lo) and the nutrients uptake. The concentrations of the macronutrients Ca, K, Mg and S in the shoot were reduced relative to the control plants, which resulted in lower contents of chlorophyll pigments. Although stress was not detected in the plants, after the analysis of stress markers like the accumulation of proline or ascorbate in the tissues, reduction of the root functionality by nanoparticles has been identified here, manifested as the effect of NM on Lo. The treatment with 50 mg l(-1) NM significantly reduced the Lo, by up to 57% of its control value, and it was reduced by up to 26% at 100 mg l(-1) NM. These results will be an important factor to take into account with regard to the applicability of NM for long-term use in crops, particularly during privative water conditions.

Trace elements and nutrients adsorption onto nano-maghemite in a contaminated-soil solution: A geochemical/statistical approach.

Two experiments were carried out to study the competition for adsorption between trace elements (TEs) and nutrients following the application of nano-maghemite (NM) (iron nano-oxide; Fe2O3) to a soil solution (the 0.01molL(-1) CaCl2 extract of a TEs-contaminated soil). In the first, the nutrients K, N, and P were added to create a set of combinations: potential availability of TEs during their interaction with NM and nutrients were studied. In the second, response surface methodology was used to develop predictive models by central composite design (CCD) for competition between TEs and the nutrients K and N for adsorption onto NM. The addition of NM to the soil solution reduced specifically the concentrations of available As and Cd, but the TE-adsorption capacity of NM decreased as the P concentration increased. The CCD provided more concise and valuable information, appropriate to estimate the behavior of NM sequestering TEs: according to the suggested models, K(+) and NH4(+) were important factors for Ca, Fe, Mg, Mn, Na, and Zn adsorption (Radj(2)=95%, except for Zn with Radj(2)=87%). The obtained information and models can be used to predict the effectiveness of NM for the stabilization of TEs, crucial during the phytoremediation of contaminated soils.

The use of olive-mill waste compost to promote the plant vegetation cover in a trace-element-contaminated soil.

The applicability of a mature compost as a soil amendment to promote the growth of native species for the phytorestoration of a mine-affected soil from a semi-arid area (SE Spain), contaminated with trace elements (As, Cd, Cu, Mn, Pb and Zn), was evaluated in a 2-year field experiment. The effects of an inorganic fertiliser were also determined for comparison. Bituminaria bituminosa was the selected native plant since it is a leguminous species adapted to the particular local pedoclimatic conditions. Compost addition increased total organic-C concentrations in soil with respect to the control and fertiliser treatments, maintained elevated available P concentrations throughout the duration of the experiment and stimulated soil microbial biomass, while trace elements extractability in the soil was rather low due to the calcareous nature of the soil and almost unaltered in the different treatments. Tissue concentrations of P and K in B. bituminosa increased after the addition of compost, associated with growth stimulation. Leaf Cu concentration was also increased by the amendments, although overall the trace elements concentrations can be considered non-toxic. In addition, the spontaneous colonisation of the plots by a total of 29 species of 15 different families at the end of the experiment produced a greater vegetation cover, especially in plots amended with compost. Therefore, the use of compost as a soil amendment appears to be useful for the promotion of a vegetation cover and the phytostabilisation of moderately contaminated soils under semi-arid conditions.

The use of a halophytic plant species and organic amendments for the remediation of a trace elements-contaminated soil under semi-arid conditions.

The halophytic shrub Atriplex halimus L. was used in a field phytoremediation experiment in a semi-arid area highly contaminated by trace elements (As, Cd, Cu, Mn, Pb and Zn) within the Sierra Minera of La Unión-Cartagena (SE Spain). The effects of compost and pig slurry on soil conditions and plant growth were determined. The amendments (particularly compost) only slightly affected trace element concentrations in soil pore water or their availability to the plants, increased soil nutrient and organic matter levels and favoured the development of a sustainable soil microbial biomass (effects that were enhanced by the presence of A. halimus) as well as, especially for slurry, increasing A. halimus biomass and ground cover. With regard to the minimisation of trace elements concentrations in the above-ground plant parts, the effectiveness of both amendments was greatest 12-16 months after their incorporation. The findings demonstrate the potential of A. halimus, particularly in combination with an organic amendment, for the challenging task of the phytostabilisation of contaminated soils in (semi-)arid areas and suggest the need for an ecotoxicological evaluation of the remediated soils. However, the ability of A. halimus to accumulate Zn and Cd in the shoot may limit its use to moderately-contaminated sites.

Accumulation of furanocoumarins by Bituminaria bituminosa in relation to plant development and environmental stress.

Bituminaria bituminosa (L.) C.H. Stirton (Fabaceae) accumulates high concentrations of the furanocoumarins (FCs) angelicin and psoralen, which protect against infection and herbivory. The effects on FC accumulation of the exposure of two populations of B. bituminosa to abiotic stress (cold, heat and drought) under field conditions were determined, as well as the effect of temperature under controlled conditions, in hydroponic culture. In field conditions, psoralen and angelicin levels in the leaf dry matter were 400-6000 and 1500-11,000 µg g(-), respectively. There were significant effects of population on the psoralen concentration and psoralen:angelicin ratio. In hydroponic culture, exposure to a diurnal temperature of 33 °C increased FC levels in population Calnegre but not in Llano del Beal, compared with plants grown at 22 °C; however, high summer temperatures in the field (>30 °C) did not coincide with the highest leaf FC levels, since the plants accumulated FCs preferentially in the fruits. Hence, leaf FC levels were higher in winter. Irrigation, to alleviate water stress in the semi-arid conditions, increased the fruit psoralen concentration but produced only minor decreases in leaf FC levels. There was a significant, positive correlation (P < 0.001) between the FC and nitrogen concentrations in the plant organs analysed (both increased in the order: fruits > growing leaves > mature leaves), reflecting their respective contributions to plant fitness. The genetically- and developmentally-regulated accumulation of FCs by B. bituminosa is altered by short-term variations in environmental conditions, particularly temperature.

Physiological responses of Bituminaria bituminosa to heavy metals.

Two hydroponic experiments were performed to study the physiological responses to heavy metals (HMs) of two populations of Bituminaria bituminosa (L.) C.H. Stirton (Fabaceae): one ("C2") from a site contaminated by HMs and one from a non-contaminated site ("LA"). In the first, we studied the effects of elevated concentrations of Zn (12 and 61 µM). Population C2 was more tolerant in terms of root and shoot growth at 61 µM Zn, relative to control plants (1 µM Zn). The similar tissue Zn levels of the two populations suggest that C2 is more tolerant of high tissue Zn. Of the parameters measured that could be related to Zn phytotoxicity (micro and macronutrients, root hydraulic activity, water-extractable Zn and organic acids), none could explain totally the superior tolerance of C2. In the second assay, the effects of Cd (4.4 µM), Cu (7.8 µM) and Zn (76 µM) on plant accumulation of the furanocoumarins (FCs) psoralen and angelicin, which function as feeding deterrents and photo-activated toxins, were assessed. For population C2, all three HMs increased the root FC concentrations, while Cd also raised shoot levels. For LA, Cu raised the root concentrations of both FCs. There was a relationship between plant stress, manifested as proline accumulation and disruption of plant water relations, and increased FC accumulation. Higher tissue levels of FCs likely provide greater protection against bacterial or fungal infection and herbivores.