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A ZnS nano-sorbent to remove copper(II) and lead(II) ions from aqueous solutions was prepared via a hydrothermal reaction and characterized by X-ray diffraction. The zinc sulfide nanoparticle size was determined to be 7.0 ± 0.22 nm. The effects of pH, light conditions, time, capacity, and interferences on the zinc sulfide ability to remove copper(II) and lead(II) ions from aqueous solutions were investigated. pH studies showed that pH 5 was the optimal value for zinc sulfide binding both copper(II) and lead(II) ions. Under ambient light, the binding of both ions occurred within the first 5 min. Binding capacities ranged from 116.2 to 243.9 mg/g for copper(II), 39.1 to 147.1 mg/g for lead(II) ions, and 36.1–79.4 mg/g for lead(II) ions in the dark over temperature range from 4 to 45 °C. The thermodynamic parameters showed that the binding process for both copper(II) and lead(II) ions was either spontaneous or close to equilibrium. Light conditions were also investigated in the context of cation interference and showed that the presence of hard cations had no effect on the binding of lead(II) ions. On the other hand, the presence of hard cations showed small decrease in the binding of copper(II) ions.

Carbon black (CB) is a nanomaterial with numerous industrial applications and high potential for integration into nano-enabled water treatment devices. However, few analytical techniques are capable of measuring CB in water at environmentally relevant concentrations. Therefore, we intended to establish a quantification method for CB with lower detection limits through utilization of trace metal impurities as analytical tracers. Various metal impurities were investigated in six commercial CB materials, and the Monarch 1000 CB was chosen as a model for further testing. The La impurity was chosen as a tracer for spICP-MS analysis based on measured concentration, low detection limits, and lack of polyatomic interferences. CB stability in water and adhesion to the spICP-MS introduction system presented a challenge that was mitigated by the addition of a nonionic surfactant to the matrix. Following optimization, the limit of detection (64 μg/L) and quantification (122 μg/L) for Monarch 1000 CB demonstrated the applicability of this approach to samples expected to contain trace amounts of CB. When compared against gravimetric analysis and UV-visible absorption spectroscopy, spICP-MS quantification exhibited similar sensitivity but with the ability to detect concentrations an order of magnitude lower. Method detection and sensitivity was unaffected when dissolved La was spiked into CB samples at environmentally relevant concentrations. Additionally, a more complex synthetic matrix representative of drinking water caused no appreciable impact to CB quantification. In comparison to existing quantification techniques, this method has achieved competitive sensitivity, a wide working range for quantification, and high selectivity for tracing possible release of CB materials with known metal contents.

In this study, we investigated the effects of citric acid (CA) coated copper oxide nanoparticles (CuO NPs) and their application method (foliar or soil exposure) on the growth and physiology of soybean (Glycine max). After nanomaterials exposure via foliar or soil application, Cu concentration was elevated in the roots, leaves, stem, pod, and seeds; distribution varied by plant organ and surface coating. Foliar application of CuO NPs at 300 mg/L and CuO-CA NPs at 75 mg/L increased soybean yield by 169.5% and 170.1%, respectively. In contrast, foliar and soil exposure to ionic Cu with all treatments (75 and 300 mg/L) had no impact on yield. Additionally, CuO-CA NPs at 300 mg/L significantly decreased Cu concentration in seeds by 46.7%, compared to control, and by 44.7%, compared to equivalent concentration of CuO NPs. Based on the total Cu concentration, CuO NPs appeared to be more accessible for plant uptake, compared to CuO-CA NPs, inducing a decrease in protein content by 56.3% and inhibiting plant height by 27.9% at 300 mg/kg under soil exposure. The translocation of Cu from leaf to root and from the root to leaf through the xylem was imaged by two-photon microscopy. The findings indicate that citric acid coating reduced CuO NPs toxicity in soybean, demonstrating that surface modification may change the toxic properties of NPs. This research provides direct evidence for the positive effects of CuO-CA NPs on soybean, including accumulation and in planta transfer of the particles, and provides important information when assessing the risk and the benefits of NP use in food safety and security.

The application of nanomaterials as a method to overcome plant stress and increase crop yield is relatively new as compared to the use of fertilizers and pesticides in agricultural production. In t...

The accumulation of engineered nanomaterials (ENMs) will increase as more applications are discovered for their unique properties and characteristics. Additionally, the presence of nanomaterials in...

Bulk Cu compounds such as Cu(OH)2 are extensively used as pesticides in agriculture. Recent investigations suggest that Cu-based nanomaterials can replace bulk materials reducing the environmental impacts of Cu. In this study, stress responses of alfalfa (Medicago sativa L.) seedlings to Cu(OH)2 nanoparticle or compounds were evaluated. Seeds were immersed in suspension/solutions of a Cu(OH)2 nanoform, bulk Cu(OH)2, CuSO4, and Cu(NO3)2 at 25 and 75 mg/L. Six days later, the germination, seedling growth, and the physiological and biochemical responses of sprouts were evaluated. All Cu treatments significantly reduced root elongation (average = 63%). The ionic compounds at 25 and 75 mg/L caused a reduction in all elements analyzed (Ca, K, Mg, P, Zn, and Mn), excepting for S, Fe and Mo. The bulk-Cu(OH)2 treatment reduced K (48%) and P (52%) at 75 mg/L, but increased Zn at 25 (18%) and 75 (21%) mg/L. The nano-Cu(OH)2 reduced K (46%) and P (48%) at 75 mg/L, and also P (37%) at 25 mg/L, compared with control. Confocal microscopy images showed that all Cu compounds, at 75 mg/L, significantly reduced nitric oxide, concurring with the reduction in root growth. Nano Cu(OH)2 at 25 mg/L upregulated the expression of the Cu/Zn superoxide dismutase gene (1.92-fold), while ionic treatments at 75 mg/L upregulated (∼10-fold) metallothionein (MT) transcripts. Results demonstrated that nano and bulk Cu(OH)2 compounds caused less physiological impairments in comparison to the ionic ones in alfalfa seedlings.

Metallic nanoparticles (NPs) are being extensively used in electronics, cosmetics, sporting goods, and medicine. Only recently, use of metallic nanomaterials extended to agricultural production, which could lead to their buildup in arable lands and affect soil productivity. Several investigations, with different NPs and under different exposure conditions, have been conducted to understand the effects of metallic NPs on terrestrial plants. These studies have propelled the application of NPs as agrochemicals that are able to supply nutrients, combat pests and weeds, and alleviate abiotic stress. The applications of novel, high-throughput technologies and advanced spectroscopic techniques have been of great help to understand the complex metabolic responses of plants to NP exposure. However, there is still limited information about the interactions of metallic NPs with plant molecules and soil components and their repercussions on agricultural productivity. This work discusses the benefits and disadvantages that metallic NPs might represent for crops. Additionally, the effects of the metallic NPs on plant physiology are analyzed by scrutinizing recent spectroscopic and gene expression/transcriptomic studies.

The recent application of nano copper (Cu) compounds in the agrosystem has shown potential to improve the physiological performance and agronomical parameters of crops. We grew alfalfa (Medicago sativa) in potting mix amended with bulk, nano, and ionic Cu compounds at 80 and 280 mg Cu/kg; then, we evaluated plant performance at physiological and molecular levels. Plants treated with bulk/nano Cu presented better agronomical responses. The P and S content was reduced in bulk and ionic Cu-exposed plants, compared to controls (p ≤ .05). All Cu forms increased the content of Fe and Zn in roots and Fe in leaves, compared to controls (p ≤ .05). Leaf-superoxide dismutase expression was augmented ~27-fold and rubisco mRNA was unaffected in bulk/nano Cu-treated plants, compared to controls (p ≤ .05). Bulk/nano Cu incremented the relative abundance of microorganisms involved in the elemental uptake. These results indicate that nano Cu improved the physiology of alfalfa and can be considered as potential nanofertilizers.

In the present study, catalytic systems based on La-doping were developed to improve the activity and performance of CoMoS2 hydrodesulfurization catalysts. Lanthanum-doped at 5, 10, or 25% of the Co content in CoMoS2 hydrodesulfurization catalysts were synthesized through a solvothermal process. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses confirmed the catalysts were triphasic consisting of Co9S8, MoS2, and La2S3. The La doped catalysts showed enhanced catalytic activity compared with CoMoS2 synthesized under the same conditions. The CoMoS2 prepared under solvothermal synthesis conditions showed a catalytic activity of 6.80 mol g-1 s-1, however, the La0.05Co0.95MoS2 doping showed a catalytic activity of 6.51 mol g -1 s-1 whereas the La0.1Co0.9MoS2 and La0.25Co0.75MoS2 samples showed catalytic activities of 10.7 mol g-1 s-1. The reaction products indicated the major reaction pathway was direct desulfurization. The La0.25Co0.75MoS2 catalyst after one reaction cycle showed a lower amount of carbon, than the undoped CoMoS2 catalyst.

In the present study, Zea mays seedlings grown under nano Cu(OH)2 (nCu), bulk Cu(OH)2 (bCu), and ionic CuSO4 (iCu) compound exposure were harvested after six days. The nutritional profile was determined to be significantly disrupted in the roots by 1000 ppm bCu treatment, resulting in a 58.7% reduction in potassium compared to the control. In the shoots, a significant decrease of manganese was observed for 10 and 1000 ppm iCu treatments with 55.7% and 64.2% reductions, respectively. The overall protein content and catalase (CAT) enzymatic activity, however, remained unaffected in either roots or shoots, while an absence of polyphenol oxidase (PPO) activity was observed for all samples. The genetic expression of defense-related genes, metallothionein (MT), CAT, ascorbate peroxidase (APX), and PPO was assessed. The genetic expression of MT was upregulated 50-fold in roots treated with 1000 ppm bCu. There were no significant differences in CAT transcripts among the various treatments, while APX was upregulated 28 and 19-fold in shoots treated with 10 ppm bCu and 10 ppm nCu, respectively. Meanwhile, APX mRNA levels were downregulated five-fold in shoots treated with 1000 ppm iCu. Thus, indicating that the role of APX in plant defense was reinforced in seedlings exposed to low concentration of particulate Cu compounds. Remarkably, no PPO expression was found in any of the treatments and controls, which suggests this enzyme is expressed only under specific external factors or seedlings have an “immature” cascade signaling activation of the PPO system. Taken together, these results show that bCu and nCu treatments at a low concentration do not compromise vital cell machinery but rather elicit the enhancement of defense responses as observed through the increase in APX expression. Furthermore, under optimal concentrations, these Cu treatments show promise in enhancing corn defense responses, which can ultimately lead to increases in future global crop yields.

The photocatalytic degradation of simazine (SIM) was investigated using zinc oxide/graphene oxide (ZnO/GO) composite materials under visible light irradiation. The reaction kinetics was studied to optimize the reaction parameters for efficient degradation of SIM. Batch studies were performed to investigate the effects of initial reaction pH, the loading of the ZnO onto GO, and mass of catalyst on the removal of SIM from aqueous solution. A pH of 2 was determined to be the optimal reaction pH for the different ZnO-loaded GO catalysts. In addition, a mass of 40 mg of catalyst in the reaction was observed to be the most effective for the catalysts synthesized using 20 and 30 mmol of Zn2+ ions; whereas a mass of 10 mg was most effective for the ZnO/GO composite material synthesized using 10 mmol Zn2+ ions. The reaction was observed to follow a second-order kinetics for the degradation process. Furthermore, the synthesized ZnO/GO composite catalysts resulted in higher reaction rates than those observed for pure ZnO. The 30 mmol ZnO/GO composite expressed a rate of SIM degradation ten times greater than the rate observed for pure ZnO, and sixty-two times greater than the rate of photolysis. In addition, the catalyst cycling exhibited a constant photocatalytic activity for the ZnO/GO composite over three reaction cycles without the need of a conditioning cycle.

Upconversion (UC) particles are currently under intensive investigation, normally for their visible instead of ultraviolet (UV) light luminescence under near-infrared (NIR) irradiation. As a commonly studied host, NaYF4 in particular is known to have low phonon energy and high UC efficiency. Here, we present our work on enhancing UC luminescence in the UV region by adding a third dopant into a binary-doped NaYF4:Yb3+,Tm3+ host. More specifically, neodymium (Nd3+) or gadolinium (Gd3+) ions was co-doped into parent NaYF4:20mol%Yb3+,0.5mol%Tm3+ UC particles to enhance their UV UC luminescence. Experimental results demonstrated that these particles exhibited the highest degree of UV UC enhancements when co-doped with 0.05mol% Nd3+ or 2.0mol% Gd3+, expanding the potential of this type of materials into many possible applications by directly converting NIR irradiation into UV light. Fundamentally, the UV UC emission dependence of these triply doped NaYF4:Yb3+,Tm3+ particles with different Nd3+ and Gd3+ doping concentrations was investigated in terms of ground state absorption, excited state absorption and energy transfer UC mechanisms.

In the present study, titanium (IV) sulfide (TiS(2)) was synthesized and investigated for the removal of Cu(2+) and Pb(2+) ions from aqueous solutions. TiS(2) nanoparticles synthesized through a solvothermal synthesis were characterized using x-ray diffraction (XRD) and scanning electron microscopy (SEM). The average particle size for the TiS(2) material was determined to be 8.03 ± 0.98 nm from the diffraction pattern. Studies were performed to examine the effects of pH, temperature, time, and interfering ions on the binding of Cu(2+) and Pb(2+) to the TiS(2). As well isotherm studies were performed to determine the binding capacity of TiS(2) for both Cu(2+) and Pb(2+) ions. The pH profile studies showed optimal binding occurred at pH 2 for the sorption of both Cu(2+) and Pb(2+) to the TiS(2). The isotherm studies showed the adsorption capacities at temperatures of 4, 22, and 45°C for Cu(2+) were 243, 222, and 153 mg/g, respectively. An opposite trend in the adsorption was observed for Pb(2+) binding to the TiS(2). The observed binding capacities for Pb(2+) were 32, 166, and 357 mg/g, at temperatures of 4, 22, and 45°C, respectively. The thermodynamic parameters for binding showed a non-spontaneous process for the sorption of Cu(2+) whereas a spontaneous binding process was observed for the sorption of Pb(2+). Additionally, the binding of Cu(2+) on TiS(2) in the presence of interfering ions (Na(+), K(+), Mg(2+), and/or Ca(2+)) was observed to decrease at high concentrations; however, the binding of Pb(2+) was unaffected by the presence of the same cations.

Tin oxide, SnO(2), nanomaterial was synthesized and tested for the removal of Cu(2+) and Ni(2+) ions from aqueous solutions. Various parameters for the binding were investigated in batch studied, which included pH, time, temperature, and interferences. In addition, isotherm studied were performed to determine the maximum binding capacity for both Cu(2+) and Ni(2+) ions. The optimal binding pH determined from the effects of pH were to be at pH 5 for both the Cu(2+) and Ni(2+) ions. The isotherm studies were performed at temperatures of 4°C, 25 °C, and 45 °C for both the Cu(2+) and Ni(2+) ions and were found to follow the Langmuir isotherm model. The binding capacities for the Cu(2+) ions were 2.63 mg/g, 2.95 mg/g and 3.27 mg/g at the aforementioned temperatures, respectively. Whereas the binding capacities for Ni(2+) were 0.79 mg/g, 1.07 mg/g, and 1.46 mg/g at the respective temperatures. The determined thermodynamic parameters for the binding showed that the binding processes for the reactions were endothermic, as the ΔG was observed to decrease with decreasing temperatures. As well the ΔH was 28.73 kJ/mol for Cu(2+) (III) and 13.37 kJ/mol for Ni(2+). The ΔS was observed to be 92.65 J/mol for Cu(2+) and 54.53 J/mol for Ni(2+). The free energy of adsorption for the Cu(2+) was determined to be 13.99 kJ/mol and the activation energy for the binding of Ni(2+) was determined to be 8.09 KJ/mol. The activation energy data indicate that the reaction was occurring through chemisorption

The strong relationship between urinary albumin excretion (UAE) and pulse pressure (PP) in cross-sectional studies suggests that pressure pulsatility may contribute to renal microvascular injury. The longitudinal relationships between UAE and the various indices of blood pressure (BP) are not well studied. We compared the associations of UAE with the longitudinal exposure to PP and systolic, diastolic, and mean BPs. UAE was measured from 24-hour urine collections in 450 community-dwelling subjects (age: 57±15 years, 53% women, all with UAE P =0.03) but not with diastolic (β=−0.049; P =0.59) BP and with PP (β=0.216; P =0.01) but not with mean BP (β=0.032; P =0.72). Comparisons of these 2 models and stepwise regression analyses both indicated that, of the 4 longitudinal indices of BP, PP was the strongest predictor of UAE in men. The pulsatile component of BP confers the highest risk for BP-induced renal microvascular injury. Future studies should examine whether PP reduction provides additional renoprotection beyond that attained by conventional BP goals alone.

Microorganisms effect with probiotic potential in water quality and growth of the shrimp Litopenaeus vannamei (Decapoda: Penaeidae) in intensive culture. The use of probiotics has gained accep- tance in aquaculture, particularly in maintaining water quality and enhancing growth in organisms. This study analyzed the effect of the commercial (EM TM , Japan) natural product composed by (Rhodopseudomonas palus- tris, Lactobacillus plantarum, Lactobacillus casei and Saccharomyces cerevisiae) added to the water, in order to determine its effect in water quality, sediment and growth of L. vannamei under intensive culture. The evaluation included three treatments with a weekly addition of EM: i) tanks without probiotics (C), ii) tanks with a dose of 4L/ha (EM1) and iii) tanks with a dose of 10L/ha (EM2). The treatment C was carried out three times, while treatments EM1 and EM2 were carried out four times. A total of 4 350 shrimps were measured for total length and weight, to calculate total and porcentual weight gain, daily weight gain, specific growth rate (TCE), and food conversion factor (FCA); besides, the survival rate was estimated. The use of probiotics allowed a shorter harvest time in treatments EM1 (90d) and EM2 (105d) with relation to the treatment C (120d). Treatments EM1 and EM2 were within the recommended intervals for culture, with respect to treatment C. The use of probiotic bacteria significantly regulated pH (EM1, 8.03±0.33; EM2, 7.77±0.22; C, 9.08±0.35) and reduced nitrate con- centration (EM1, 0.64±0.25mg/L; EM2, 0.39±0.26mg/L; C, 0.71mg/L). Water pH mostly explained the variance with respect to the treatments. Treatment EM2 presented the greatest removal of organic matter (1.77±0.45%), whereas the contents of extractable phosphorus increased significantly in treatment EM1 with 21.6±7.99mg/kg and in treatment EM2 with 21.6±8.45mg/kg with control relation (14.3±5.47). The shrimp growth was influ- enced by dissolved oxygen, salinity and pH in the sediment, establishing that salinity was the most important variable in the weight with a negative association. Treatment EM1 recorded an improved TCE (2.69±0.35%/d) and FCA (1.46±0.20) with relation to the control treatment (TCE, 1.88±0.25%/d; FCA, 2.13±0.48). Survival was significantly greater in treatments containing probiotics with 61±8.76% and 60±10.5% for EM1 and EM2, respectively. This study indicated the positive effect obtained with the use of this commercial probiotic, to improve culture conditions and growth parameters in an intensive culture of L. vannamei. Rev. Biol. Trop. 61 (3): 1215-1228. Epub 2013 September 01.

Premise of the study: The Million Orchid Project at Fairchild Tropical Botanic Garden is an initiative to propagate native orchids for reintroduction into Miami’s urban landscapes. The aim of this study was to develop microsatellites for Encyclia tampensis and Cyrtopodium punctatum (Orchidaceae). Methods and Results: Ten microsatellites were developed for each species. For E. tampensis sampled from the natural population, allele numbers ranged from one to four, with an average observed heterozygosity (Ho) of 0.314 and average expected heterozygosity (He) of 0.281. For the individuals from cultivation, allele numbers ranged from one to six, with an average Ho of 0.35 and an average He of 0.224. For C. punctatum, allele numbers ranged from one to three, with an average Ho of 0.257 and an average He of 0.272. Conclusions: These microsatellites will be used to assess the genetic diversity of natural and cultivated populations with the intention of guiding genetic breeding under the Million Orchid Project.