Targeting Metal Impurities for the Detection and Quantification of Carbon Black Particles in Water via spICP-MS.

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.

Tomato Fruit Nutritional Quality Is Altered by the Foliar Application of Various Metal Oxide Nanomaterials.

Carbohydrates and phytonutrients play important roles in tomato fruit's nutritional quality. In the current study, Fe3O4, MnFe2O4, ZnFe2O4, Zn0.5Mn0.5Fe2O4, Mn3O4, and ZnO nanomaterials (NMs) were synthesized, characterized, and applied at 250 mg/L to tomato plants via foliar application to investigate their effects on the nutritional quality of tomato fruits. The plant growth cycle was conducted for a total of 135 days in a greenhouse and the tomato fruits were harvested as they ripened. The lycopene content was initially reduced at 0 stored days by MnFe2O4, ZnFe2O4, and Zn0.5Mn0.5Fe2O4; however, after a 15-day storage, there was no statistical difference between the treatments and the control. Moreover, the ß-carotene content was also reduced by Zn0.5Mn0.5Fe2O4, Mn3O4, and ZnO. The effects of the Mn3O4 and ZnO carried over and inhibited the ß-carotene after the fruit was stored. However, the total phenolic compounds were increased by ZnFe2O4, Zn0.5Mn0.5Fe2O4, and ZnO after 15 days of storage. Additionally, the sugar content in the fruit was enhanced by 118% and 111% when plants were exposed to Mn3O4 and ZnO, respectively. This study demonstrates both beneficial and detrimental effects of various NMs on tomato fruit quality and highlights the need for caution in such nanoscale applications during crop growth.

Soil and foliar exposure of soybean (Glycine max) to Cu: Nanoparticle coating-dependent plant responses.

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.

A double-edged effect of manganese-doped graphene quantum dots on salt-stressed Capsicum annuum L.

The objective of the current study is to evaluate both the positive and negative effects of manganese-doped graphene quantum dots (GQD-Mn) on Capsicum annuum L. grown under salt stress. GQD-Mn was synthesized, characterized, and foliar-applied (250 mg/L, 120 mg/L, 60 mg/L) to C. annuum L. before and after the flowering stage, during which 100 mM of NaCl solution was introduced into the soil as salt stress. Controls were designed as absolute control (no nanomaterials or salt) and negative control (no nanomaterials only salt). Herein, we report that GQD-Mn offset the reduction of fruit production in salt-stressed C. annuum L. by around 40 %. However, based on a comprehensive analysis of normal alkanes (n-alkane) using gas chromatography-mass spectrometry (GC-MS), we also observed that the leaf epicuticular wax profile was disturbed by GQD-Mn, as the concentration of long-chain n-alkanes was increased. Meanwhile, the content of magnesium (Mg) and zinc (Zn) indicated a potential promoted photosynthesis activity in C. annuum L leaves. We hypothesize that the optical properties of GQD-Mn allow leaves to utilize light more efficiently, thus improving photosynthetic activities in plants to acclimate salt stress. But the increased light usage also induced heat stress on the leaf surfaces, which caused n-alkanes changes. Our results provided a unique perspective on nano-plant interaction that value both beneficial and toxic effects of nanomaterials, especially when evaluating the safety of nano-enabled agriculture in areas facing harsh environmental conditions such as salinity.