Single particle ICP-MS method development for the determination of plant uptake and accumulation of CeO2 nanoparticles.

Cerium dioxide nanoparticles (CeO2NPs) are among the most broadly used engineered nanoparticles that will be increasingly released into the environment. Thus, understanding their uptake, transportation, and transformation in plants, especially food crops, is critical because it represents a potential pathway for human consumption. One of the primary challenges for the endeavor is the inadequacy of current analytical methodologies to characterize and quantify the nanomaterial in complex biological samples at environmentally relevant concentrations. Herein, a method was developed using single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) technology to simultaneously detect the size and size distribution of particulate Ce, particle concentration, and dissolved cerium in the shoots of four plant species including cucumber, tomato, soybean, and pumpkin. An enzymatic digestion method with Macerozyme R-10 enzyme previously used for gold nanoparticle extraction from the tomato plant was adapted successfully for CeO2NP extraction from all four plant species. This study is the first to report and demonstrate the presence of dissolved cerium in plant seedling shoots exposed to CeO2NPs hydroponically. The extent of plant uptake and accumulation appears to be dependent on the plant species, requiring further systematic investigation of the mechanisms.

Characterization of gold nanoparticle uptake by tomato plants using enzymatic extraction followed by single-particle inductively coupled plasma-mass spectrometry analysis.

Plant uptake and accumulation of nanoparticles (NPs) represent an important pathway for potential human expose to NPs. Consequently, it is imperative to understand the uptake of accumulation of NPs in plant tissues and their unique physical and chemical properties within plant tissues. Current technologies are limited in revealing the unique characteristics of NPs after they enter plant tissues. An enzymatic digestion method, followed by single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) analysis, was developed for simultaneous determination of gold NP (AuNP) size, size distribution, particle concentration, and dissolved Au concentration in tomato plant tissues. The experimental results showed that Macerozyme R-10 enzyme was capable of extracting AuNPs from tomato plants without causing dissolution or aggregation of AuNPs. The detection limit for quantification of AuNP size was 20 nm, and the AuNP particle concentration detection limit was 1000 NPs/mL. The particle concentration recoveries of spiked AuNPs were high (79-96%) in quality control samples. The developed SP-ICP-MS method was able to accurately measure AuNP size, size distribution, and particle concentration in the plant matrix. The dosing study indicated that tomato can uptake AuNPs as intact particles without alternating the AuNP properties.

Preparation of green biosorbent using rice hull to preconcentrate, remove and recover heavy metal and other metal elements from water.

Sodium hydroxide treated rice hulls were investigated to preconcentrate, remove, and recover metal ions including Be2+, Al3+, Cr3+, Co2+, Ni2+, Cu2+, Zn2+, Sr2+, Ag+, Cd2+, Ba2+, and Pb2+ in both batch mode and column mode. Sodium hydroxide treatment significantly improved the removal efficiency for all metal ions of interest compared to the untreated rice hull. The removal kinetics were extremely fast for Co, Ni, Cu, Zn, Sr, Cd, and Ba, which made the treated rice hull a promising economic green adsorbent to preconcentrate, remove, and recover low-level metal ions in column mode at relatively high throughput. The principal removal mechanism is believed to be the electrostatic attraction between the negatively charged rice hulls and the positively charged metal ions. pH had a drastic impact on the removal for different metal ions and a pH of 5 worked best for most of the metal ions of interest. Processed rice hulls provide an economic alternative to costly resins that are currently commercially available products designed for metal ion preconcentration for trace metal analysis, and more importantly, for toxic heavy metal removal and recovery from the environment.

Preliminary studies of a novel multifunctional wide-bore electrophoresis system.

This paper presents the results obtained from a novel multifunctional analysis platform established on the basis of wide-bore electrophoresis (WBE) and CE. The WBE­CE system integrated various analytical steps including separation, transfer, reaction, detection, and storage into a single system. During the WBE­CE process, a distinct three-electrode format was adopted to continuously separate and transfer samples between WBE and CE without the interruption of switching on-and-off the power suppliers. This continuous mode of operation also helped to eliminate the need for exactly timing the transfer of specific samples zone from WBE to CE and avoided the danger of missing specific samples. Samples representing mixtures of acids, bases, or proteins were analyzed on this system for evaluating its feasibility and applicability. The results indicated that the resolution achieved on this WBE­CE system was better than either the WBE or the CE alone. Further, samples transferred out of the WBE system could participate in online reaction, such as enzymatic reaction in the CE. Alternatively, samples from the WBE system could be transferred out and stored offline in a vial for post-transfer reaction. The results demonstrated that this WBE­CE system has the potential to be a multifunctional platform for a range of applications.

Effect of oxidant demand on the release and degradation of microcystin-LR from Microcystis aeruginosa during oxidation.

In this research, the release and degradation of intracellular microcystin-LR (MC-LR) due to oxidation of Microcystis aeruginosa (M. aeruginosa) was examined kinetically. Brief exposure to free chlorine with no measureable oxidant exposure was demonstrated to be sufficient to induce rapid release of intracellular MC-LR from M. aeruginosa. Thus, in a water treatment plant, there is currently no level of prechlorination that can be assumed to be safe, since very low preoxidation prior to filtration and no measureable free chlorine residual may still observe the release and buildup of extracellular MC-LR. Higher chlorine dosages resulting in a measureable exposure or CT (concentration times contact time) cause more rapid release and oxidation of the intracellular toxins. Further, the rate of release of MC-LR with intermediate oxidant dosages were shown to be initially rapid, but then slowed to a lower release rate due to an as yet undetermined mechanism. While free chlorine was reactive with the extracellular MC-LR, the monochloramine resulting from the consumption of the free chlorine by ammonia was not. Consideration of the ammonia concentration and the chlorine dosage relative to the chlorination breakpoint dosages is important for utilities assessing the impact of prechlorination of water containing cyanobacteria. MC-LR, once released, was rapidly oxidized by permanganate resulting in only negligible buildup of extracellular toxins.

Urinary metallomics as a novel biomarker discovery platform: Breast cancer as a case study.

BACKGROUND: Urinary metallomics is presented here as a new "omics" approach that aims to facilitate personalized cancer screening and prevention by improving our understanding of urinary metals in disease. METHODS: Twenty-two urinary metals were examined with inductively-coupled plasma-mass spectrometry in 138 women newly diagnosed with breast cancer and benign conditions. Urinary metals from spot urine samples were adjusted to renal dilution using urine specific gravity. RESULTS: Two urinary metals, copper (P-value=0.036) and lead (P-value=0.003), were significantly increased in the urine of breast cancer patients. A multivariate model that comprised copper, lead, and patient age afforded encouraging discriminatory power (AUC: 0.728, P-value<0.0005), while univariate models of copper (61.7% sensitivity, 50.0% specificity) and lead (76.6% sensitivity, 51.2% specificity) at optimized cutoff thresholds compared favorably with other breast cancer diagnostic modalities such as mammography. Correlations found among various metals suggested potential geographic and dietary influences on the urine metallome that warrant further investigation. CONCLUSIONS: This proof-of-concept work introduces urinary metallomics as a noninvasive, potentially transformative "omics" approach to early cancer detection. Urinary copper and lead have also been preliminarily identified as potential breast cancer biomarkers.