Therapeutic Delivery of Nanoscale Sulfur to Suppress Disease in Tomatoes: In Vitro Imaging and Orthogonal Mechanistic Investigation.

Nanoscale sulfur can be a multifunctional agricultural amendment to enhance crop nutrition and suppress disease. Pristine (nS) and stearic acid coated (cS) sulfur nanoparticles were added to soil planted with tomatoes (Solanum lycopersicum) at 200 mg/L soil and infested with Fusarium oxysporum. Bulk sulfur, ionic sulfate, and healthy controls were included. Orthogonal end points were measured in two greenhouse experiments, including agronomic and photosynthetic parameters, disease severity/suppression, mechanistic biochemical and molecular end points including the time-dependent expression of 13 genes related to two S bioassimilation and pathogenesis-response, and metabolomic profiles. Disease reduced the plant biomass by up to 87%, but nS and cS amendment significantly reduced disease as determined by area-under-the-disease-progress curve by 54 and 56%, respectively. An increase in planta S accumulation was evident, with size-specific translocation ratios suggesting different uptake mechanisms. In vivo two-photon microscopy and time-dependent gene expression revealed a nanoscale-specific elemental S bioassimilation pathway within the plant that is separate from traditional sulfate accumulation. These findings correlate well with time-dependent metabolomic profiling, which exhibited increased disease resistance and plant immunity related metabolites only with nanoscale treatment. The linked gene expression and metabolomics data demonstrate a time-sensitive physiological window where nanoscale stimulation of plant immunity will be effective. These findings provide mechanistic understandings of nonmetal nanomaterial-based suppression of plant disease and significantly advance sustainable nanoenabled agricultural strategies to increase food production.

Seed Biofortification by Engineered Nanomaterials: A Pathway To Alleviate Malnutrition?

Micronutrient deficiencies in global food chains are a significant cause of ill health around the world, particularly in developing countries. Agriculture is the primary source of nutrients required for sound health, and as the population has continued to grow, the agricultural sector has come under pressure to improve crop production, in terms of both quantity and quality, to meet the global demands for food security. The use of engineered nanomaterial (ENM) has emerged as a promising technology to sustainably improve the efficiency of current agricultural practices as well as overall crop productivity. One promising approach that has begun to receive attention is to use ENM as seed treatments to biofortify agricultural crop production and quality. This review highlights the current state of the science for this approach as well as critical knowledge gaps and research needs that must be overcome to optimize the sustainable application of nano-enabled seed fortification approaches.

Improvement of nutrient elements and allicin content in green onion (Allium fistulosum) plants exposed to CuO nanoparticles.

With the exponential growth of nanomaterial production in the last years, nano copper (Cu)-based compounds are gaining more consideration in agriculture since they can work as pesticides or fertilizers. Chinese scallions (Allium fistulosum), which are characterized by their high content of the antioxidant allicin, were the chosen plants for this study. Spectroscopic and microscopic techniques were used to evaluate the nutrient element, allicin content, and enzyme antioxidant properties of scallion plants. Plants were harvested after growing for 80 days at greenhouse conditions in soil amended with CuO particles [nano (nCuO) and bulk (bCuO)] and CuSO4 at 75-600 mg/kg]. Two-photon microscopy images demonstrated the particulate Cu uptake in nCuO and bCuO treated roots. In plants exposed to 150 mg/kg of the Cu-based compounds, root Cu content was higher in plants treated with nCuO compared with bCuO, CuSO4, and control (p ≤ 0.05). At 150 mg/kg, nCuO increased root Ca (86%), root Fe (71%), bulb Ca (74%), and bulb Mg (108%) content, compared with control (p ≤ 0.05). At the same concentration, bCuO reduced root Ca (67%) and root Mg (33%), compared with control (p ≤ 0.05). At all concentrations, nCuO and CuSO4 increased leaf allicin (56-187% and 42-90%, respectively), compared with control (p ≤ 0.05). The antioxidant enzymes were differentially affected by the Cu-based treatments. Overall, the data showed that nCuO enhances nutrient and allicin contents in scallion, which suggests they might be used as a nanofertilizer for onion production.

Zinc oxide nanoparticles alleviate drought-induced alterations in sorghum performance, nutrient acquisition, and grain fortification.

Drought is a major environmental event affecting crop productivity and nutritional quality, and potentially, human nutrition. This study evaluated drought effects on performance and nutrient acquisition and distribution in sorghum; and whether ZnO nanoparticles (ZnO-NPs) might alleviate such effects. Soil was amended with ZnO-NPs at 1, 3, and 5 mg Zn/kg, and drought was imposed 4 weeks after seed germination by maintaining the soil at 40% of field moisture capacity. Flag leaf and grain head emergence were delayed 6-17 days by drought, but the delays were reduced to 4-5 days by ZnO-NPs. Drought significantly (p < 0.05) reduced (76%) grain yield; however, ZnO-NP amendment under drought improved grain (22-183%) yield. Drought inhibited grain nitrogen (N) translocation (57%) and total (root, shoot and grain) N acquisition (22%). However, ZnO-NPs (5 mg/kg) improved (84%) grain N translocation relative to the drought control and restored total N levels to the non-drought condition. Shoot uptake of phosphorus (P) was promoted (39%) by drought, while grain P translocation was inhibited (63%); however, ZnO-NPs lowered total P acquisition under drought by 11-23%. Drought impeded shoot uptake (45%), grain translocation (71%) and total acquisition (41%) of potassium (K). ZnO-NP amendment (5 mg/kg) to drought-affected plants improved total K acquisition (16-30%) and grain K (123%), relative to the drought control. Drought lowered (32%) average grain Zn concentration; however, ZnO-NP amendments improved (94%) grain Zn under drought. This study represents the first evidence of mitigation of drought stress in full-term plants solely by exposure to ZnO-NPs in soil. The ability of ZnO-NPs to accelerate plant development, promote yield, fortify edible grains with critically essential nutrients such as Zn, and improve N acquisition under drought stress has strong implications for increasing cropping systems resilience, sustaining human/animal food/feed and nutrition security, and reducing nutrient losses and environmental pollution associated with N-fertilizers.

Nanoparticle and Ionic Zn Promote Nutrient Loading of Sorghum Grain under Low NPK Fertilization.

This study evaluated the effects of ZnO nanoparticles (NP) or Zn salt amendment on sorghum yield, macronutrient use efficiency, and grain Zn-enrichment. Amendments were through soil and foliar pathways, under "low" and "high" levels of nitrogen, phosphorus, and potassium (NPK). In soil and foliar amendments, grain yield was significantly (p ≤ 0.05) increased by both Zn types, albeit insignificantly with soil-applied Zn at low NPK. Across NPK levels and Zn exposure pathways, both Zn types increased N and K accumulation relative to control plants. Compared to N and K, both Zn types had a mixed effect on P accumulation, depending on NPK level and Zn exposure pathway, and permitted greater soil P retention. Both Zn types significantly (p ≤ 0.05) increased grain Zn content, irrespective of exposure pathway. These findings suggest a nanoenabled strategy for enhancing crop productivity, grain nutritional quality, and N use efficiency based on Zn micronutrient amendments, with potential implications for improved human and environmental health.

Surface coating changes the physiological and biochemical impacts of nano-TiO2 in basil (Ocimum basilicum) plants.

Little is known about the effects of surface coating on the interaction of engineered nanoparticles (ENPs) with plants. In this study, basil (Ocimum basilicum) was cultivated for 65 days in soil amended with unmodified, hydrophobic (coated with aluminum oxide and dimethicone), and hydrophilic (coated with aluminum oxide and glycerol) titanium dioxide nanoparticles (nano-TiO2) at 125, 250, 500, and 750 mg nano-TiO2 kg-1 soil. ICP-OES/MS, SPAD meter, and UV/Vis spectrometry were used to determine Ti and essential elements in tissues, relative chlorophyll content, carbohydrates, and antioxidant response, respectively. Compared with control, hydrophobic and hydrophilic nano-TiO2 significantly reduced seed germination by 41% and 59%, respectively, while unmodified and hydrophobic nano-TiO2 significantly decreased shoot biomass by 31% and 37%, respectively (p ≤ 0.05). Roots exposed to hydrophobic particles at 750 mg kg-1 had 87% and 40% more Ti than the pristine and hydrophilic nano-TiO2; however, no differences were found in shoots. The three types of particles affected the homeostasis of essential elements: at 500 mg kg-1, unmodified particles increased Cu (104%) and Fe (90%); hydrophilic increased Fe (90%); while hydrophobic increased Mn (339%) but reduced Ca (71%), Cu (58%), and P (40%). However, only hydrophobic particles significantly reduced root elongation by 53%. Unmodified, hydrophobic, and hydrophilic particles significantly reduced total sugar by 39%, 38%, and 66%, respectively, compared with control. Moreover, unmodified particles significantly decreased reducing sugar (34%), while hydrophobic particles significantly reduced starch (35%). Although the three particles affected basil plants, coated particles impacted the most its nutritional quality, since they altered more essential elements, starch, and reducing sugars.

Cerium dioxide and zinc oxide nanoparticles alter the nutritional value of soil cultivated soybean plants.

The aim of this study was to determine nutrient elements in soybean (Glycine max) plants cultivated in farm soil amended with nCeO2 at 0-1000 mg kg(-1) and nZnO at 0-500 mg kg(-1). Digested samples were analyzed by ICP-OES/MS. Compared to control, pods from nCeO2 at 1000 mg kg(-1) had significantly less Ca but more P and Cu, while pods from 100 mg kg(-1)nZnO had more Zn, Mn, and Cu. Plants treated with nZnO showed significant correlations among Zn, P, and S in pods with Zn in roots. Correlations among pod Zn/root Zn was r = 0.808 (p ≤ 0.01) and pod P/root P was r = 0.541 (p ≤ 0.05). The correlation among pod S/root S was r = -0.65 (p ≤ 0.01). While nCeO2 treatments exhibited significant correlations between pod Ca/root Ca (r = 0.645, p ≤ 0.05). The data suggest that nCeO2 and nZnO alter the nutritional value of soybean, which could affect the health of plants, humans, and animals.

Influence of CeO2 and ZnO nanoparticles on cucumber physiological markers and bioaccumulation of Ce and Zn: a life cycle study.

With the dramatic increase in nanotechnologies, it has become increasingly likely that food crops will be exposed to excess engineered nanoparticles (NPs). In this study, cucumber plants were grown to full maturity in soil amended with either CeO2 or ZnO NPs at concentrations of 0, 400, and 800 mg/kg. Chlorophyll and gas exchange were monitored, and physiological markers were recorded. Results showed that, at the concentrations tested, neither CeO2 nor ZnO NPs impacted cucumber plant growth, gas exchange, and chlorophyll content. However, at 800 mg/kg treatment, CeO2 NPs reduced the yield by 31.6% compared to the control (p ≤ 0.07). ICP-MS results showed that the high concentration treatments resulted in the bioaccumulation of Ce and Zn in the fruit (1.27 mg of Ce and 110 mg Zn per kg dry weight). µ-XRF images exhibited Ce in the leaf vein vasculature, suggesting that Ce moves between tissues with water flow during transpiration. To the authors' knowledge, this is the first holistic study focusing on the impacts of CeO2 and ZnO NPs in the life cycle of cucumber plants.

Use of plasma-based spectroscopy and infrared microspectroscopy techniques to determine the uptake and effects of chromium(III) and chromium(VI) on Parkinsonia aculeata.

Chromium uptake and tolerance by Mexican Palo Verde (Parkinsonia aculeata) (MPV) was studied in a six-month experiment with Cr(III) and Cr(VI) at 60 and 10 mg kg(-1), respectively. Chromium and nutrient uptake were determined by ICP-OES and changes in macromolecules were studied by infrared microspectroscopy (IMS). In the Cr(VI)-treated plants, chromium concentration increased in the roots only through the third month, while translocation to stems increased constantly throughout the six months. Cr(III) applications decreased the amount of Zn in leaves and stems (p < or = 0.05). Cr(VI) increased P and S in all plant tissues and increased Ca in roots, but decreased Ca in stems and leaves, and Mg in roots and stems. Cr(III) decreased P in stems and leaves, while both Cr ions decreased K in all MPV tissues. Relative to untreated plant tissue, the IMS revealed significant changes at 1730 cm(-1) and 845 cm(-1). Changes at 1730 cm(-1) indicated that the cortex and xylem of Cr-treated plants were more proteinaceous. Changes at 845 cm(-1) revealed higher lignifications in cortex. However, at the stem level, Cr(VI) decreased lignin deposition in xylem. The data showed that MPV could be useful in the phytoremediation of Cr in moderately impacted soils.

The extraction of gold nanoparticles from oat and wheat biomasses using sodium citrate and cetyltrimethylammonium bromide, studied by x-ray absorption spectroscopy, high-resolution transmission electron microscopy, and UV-visible spectroscopy.

Gold (Au) nanoparticles can be produced through the interaction of Au(III) ions with oat and wheat biomasses. This paper describes a procedure to recover gold nanoparticles from oat and wheat biomasses using cetyltrimethylammonium bromide or sodium citrate. Extracts were analyzed using UV-visible spectroscopy, high-resolution transmission electron microscopy (HRTEM), and x-ray absorption spectroscopy. The HRTEM data demonstrated that smaller nanoparticles are extracted first, followed by larger nanoparticles. In the fourth extraction, coating of chelating agents is visible on the extracted nanoparticles.

Coordination and speciation of cadmium in corn seedlings and its effects on macro- and micronutrients uptake.

The effect of cadmium (Cd) on both the absorption of important nutrients and the synthesis of low molecular weight thiols (LMWTs) was investigated in corn plants. The inductively coupled plasma-optical emission spectroscopy results demonstrated that the concentration of Cd in tissues (mainly in roots) increased as the concentration in the medium increased. In addition, the concentration of phosphorus increased in roots of Cd treated plants but remained at normal concentration in shoots. On the other hand, the uptake of sulfur (S) followed a similar trend as the Cd uptake. The concentration of S and the production of LMWT were found to increase significantly upon exposure to Cd. The results of the X-ray absorption spectroscopy analyses indicated that Cd within tissues was bound to S ligands with interatomic distances of 2.51-2.52 A. These results confirm a strong linkage between S uptake and the production of LMWT upon exposure to Cd.

Accumulation, speciation, and coordination of arsenic in an inbred line and a wild type cultivar of the desert plant species Chilopsis linearis (Desert willow).

This study investigated the absorption of arsenic (As), sulfur (S), and phosphorus (P) in the desert plant Chilopsis linearis (Desert willow). A comparison between an inbred line (red flowered) and wild type (white flowered) plants was performed to look for differential responses to As treatment. One month old seedlings were treated for 7 days with arsenate (As(2)O(5), As(V)) at 0, 20, and 40 mg As(V)L(-1). Results from the ICP-OES analysis showed that at 20mg As(V)L(-1), red flowered plants had 280+/-11 and 98+/-7 mg As kg(-1) dry wt in roots and stems, respectively, while white flowered plants had 196+/-30 and 103+/-13 mg As kg(-1) dry wt for roots and stems. At this treatment level, the concentration of As in leaves was below detection limits for both plants. In red flowered plants treated with 40 mg As(V)L(-1), As was at 290+/-77 and 151+/-60 mg As kg(-1) in roots and stems, respectively, and not detected in leaves, whereas white flowered plants had 406+/-36, 213+/-12, and 177+/-40 mg As kg(-1) in roots, stems, and leaves. The concentration of S increased in all As treated plants, while the concentration of P decreased in roots and stems of both types of plants and in leaves of red flowered plants. X-ray absorption spectroscopy analyses demonstrated partial reduction of arsenate to arsenite in the form of As-(SX)(3) species in both types of plants.

[Evaluation of the exposure to selenium in Los Altos de Jalisco, México]. / Evaluación de la exposición a selenio en Los Altos de Jalisco, México.

OBJECTIVE: To evaluate the exposure to selenium in drinking water in Los Altos de Jalisco (Jalisco State Heights). MATERIALS AND METHODS: The concentration of selenium was determined in 125 water wells, and the exposure doses to selenium were estimated for babies, children and adults. RESULTS: The estimated values of the exposure doses to selenium and total intake of selenium were in the following ranges, respectively: (a) babies: 1.3-6.7 microg/kg/d and 12.6-67.2 microg/d; (b) children: 0.8-4.5 microg/kg/d and 16.8-89.6 microg/d, (c) adults: 0.6-3.0 microg/kg/d and 33.6-179.2 microg/d. CONCLUSIONS: The estimated exposure levels to selenium were higher than those recommended as optimum by international health organizations, representing a potential health risk. Nevertheless, estimated values are not high enough to produce selenosis.

Evaluación de la exposición a selenio en Los Altos de Jalisco, México / Evaluation of the exposure to selenium in Los Altos de Jalisco, México

OBJETIVO: Evaluar la exposición a selenio (Se) vía agua potable en los habitantes de Los Altos de Jalisco. MATERIAL Y MÉTODOS: Se determinó la concentración de Se en 125 pozos y se estimaron los niveles de exposición a Se en bebés, niños y adultos. RESULTADOS: La dosis de exposición y la ingestión de Se vía agua potable variaron en los siguientes rangos: a) bebés: 1.3-6.7 µg/kg/d y 12.6-67.2 µg/d; b) niños: 0.8-4.5 µg/kg/d y 16.8-89.6 µg/d; c) adultos: 0.6-3.0 µg/kg/d y 33.6-179.2 µg/d. CONCLUSIONES: En este caso, la exposición a Se representa un riesgo potencial para la salud de la población, ya que en la mayoría de los casos es mayor que la recomendada por organismos internacionales de salud. Sin embargo, no es tan alta como para esperar la ocurrencia de selenosis.

OBJECTIVE: To evaluate the exposure to selenium in drinking water in Los Altos de Jalisco (Jalisco State Heights). MATERIALS AND METHODS: The concentration of selenium was determined in 125 water wells, and the exposure doses to selenium were estimated for babies, children and adults. RESULTS: The estimated values of the exposure doses to selenium and total intake of selenium were in the following ranges, respectively: (a) babies: 1.3-6.7 µg/kg/d and 12.6-67.2 µg/d; (b) children: 0.8-4.5 µg/kg/d and 16.8-89.6 µg/d, (c) adults: 0.6-3.0 µg/kg/d and 33.6-179.2 µg/d. CONCLUSIONS: The estimated exposure levels to selenium were higher than those recommended as optimum by international health organizations, representing a potential health risk. Nevertheless, estimated values are not high enough to produce selenosis.

Using mummichog (Fundulus heteroclitus) arrays to monitor the effectiveness of remediation at a superfund site in Charleston, South Carolina, U.S.A.

We previously developed a cDNA array for mummichogs (Fundulus heteroclitus), an estuarine minnow, that is targeted for identifying differentially expressed genes from exposure to polycyclic aromatic hydrocarbons and several metals, including chromium. A chromium-contaminated Superfund site at Shipyard Creek in Charleston, South Carolina, USA, is undergoing remediation, providing us a unique opportunity to study the utility of arrays for monitoring the effectiveness of site remediation. Mummichogs were captured in Shipyard Creek in Charleston prior to remediation (2000) and after remediation began (2003 and 2005). Simultaneously, mummichogs were collected from a reference site at the Winyah Bay National Estuarine Research Reserve (NERR) in Georgetown, South Carolina, USA. The hepatic gene expression pattern of fish captured at Shipyard Creek in 2000 showed wide differences from the fish captured at NERR in 2000. Interestingly, as remediation progressed the gene expression pattern of mummichogs captured at Shipyard Creek became increasingly similar to those captured at NERR. The arrays acted as multidimensional biomarkers as the number of differentially expressed genes dropped from 22 in 2000 to four in 2003, and the magnitude of differential expression dropped from 3.2-fold in 2000 to no gene demonstrating a difference over 1.5-fold in 2003. Furthermore, the arrays indicated changes in the bioavailability of chromium caused by hydraulic dredging in the summer of 2005. This research is, to our knowledge, the first report using arrays as biomarkers for a weight-of-evidence hazard assessment and demonstrates that arrays can be used as multidimensional biomarkers to monitor site mitigation because the gene expression profile is associated with chromium bioavailability and body burden.

Spectroscopic study of the impact of arsenic speciation on arsenic/phosphorus uptake and plant growth in tumbleweed (Salsola kali).

This manuscript reports the toxic effects of As2O3 (arsenic trioxide) and As2O5 (arsenic pentoxide) on S. kali as well as the arsenic and phosphate uptake and arsenic coordination within plant tissues. Plants were germinated and grown for 15 days on a Hoagland-modified medium containing either As(III) (arsenic trioxide) or As(V) (arsenic pentoxide). Subsequently, the seedlings were measured and analyzed using inductively coupled plasma optical emission spectroscopy and X-ray absorption spectroscopy techniques. Plants stressed with 2 mg L(-1) of whichever As(III) or As(V) concentrated 245 +/- 19, 30 +/- 1, and 60 +/- 3 mg As kg(-1) dry weight or 70 +/- 6, 10 +/- 0.3, and 27 +/- 3 mg As kg(-1) dry weight in roots, stems, and leaves, respectively. Arsenate was less toxic, and more As translocation occurred from the roots to the leaves. All treatments reduced P concentration at root level; however, only As(V) at 2 and 4 mg L(-1) reduced P concentration at leaf level. Regardless the arsenic species supplied to the plants, arsenic was found in plant tissues as As(III) coordinated to three sulfur ligands with an interatomic distance of approximately 2.25 angstroms.

Production of low-molecular weight thiols as a response to cadmium uptake by tumbleweed (Salsola kali).

Tumbleweed (Salsola kali) is a desert plant species that has shown to be a potential Cd hyperaccumulator. In this study, the production of low-molecular weight thiols (LMWT) as a response to cadmium stress was determined in hydroponically grown seedlings exposed to 0, 45, 89, and 178 microM Cd(2+). The treatment of 89 microM Cd(2+) was tested alone and supplemented with an equimolar concentration of ethylenediaminetetraacetic acid (EDTA) to determine the effect of this chelating agent on Cd uptake and thiols production. After 6 days of growth, the Cd concentration in plant tissues was determined by using inductively coupled plasma/optical emission spectroscopy (ICP/OES). Results indicated that Cd uptake by plants was concentration-dependent. Plants treated with 178 microM Cd(2+), had 10+/-0.62, 9.7+/-1.4, and 4.3+/-0.83 mmol Cd kg(-1) dry tissue in roots, stems, and leaves, respectively. The production of thiols was dependent on Cd concentration in tissues. According to the stoichiometry performed, plants treated with Cd concentrations up to 178 muM produced 0.131+/-0.02, and 0.087+/-0.012 mmol SH per mmol Cd present in roots and stems. In leaves, the production of thiols decreased at the highest Cd concentration tested. Thus, up to 89 microM Cd in the media, 0.528+/-0.004 mmol SH per mmol Cd in leaf tissues were produced. EDTA equimolar to Cd reduced both Cd uptake and thiols production. Catalase activity (CAT) (EC 1.11.1.6) was significantly depressed at the lowest Cd concentration. None of the conditions tested affected biomass or plant elongation.