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Control of toxic or carcinogenic disinfection byproduct (DBP) formation in drinking water is critical in an effort to improve drinking water safety and safeguard public health, due to the elevation...

This study investigated uptake of two organic compounds including hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and exogenous caffeine by tomato (The uptake of two organic compounds (RDX and exogenous caffeine) was examined in three crop plants (corn, wheat, and tomato). There have not been any uptake studies on exogenous caffeine and also we do not have good data for the uptake of RDX by these three crop plants. The estimated sap concentration factor from these experiments fills the gap in the data for developing predictive models for uptake of emerging contaminants. A novel rapid freeze–thaw/centrifugation extraction method followed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was used to analyze the samples.

Loxosceles reclusa, or brown recluse spider, is a harmful household spider whose habitat extends throughout the Midwest in the USA and other regions in the world. The pheromones and other biomolecules that facilitate signaling for brown recluses and other spider species are poorly understood. A rapid and sensitive method is needed to analyze airborne spider signaling biomolecules to better understand the structure and function of these biochemicals in order to control the population of the spiders. In this study, we developed a novel headspace solid-phase microextraction (HS-SPME)-GC/MS method to analyze potential pheromones and biomolecules emitted by the brown recluse spider. The method is highly selective and sensitive for biomolecule identification and quantification from a single live spider. Using this novel non-destructive HS-SPME-GC/MS technique, we identified 11 airborne biomolecules, including 4-methylquinazoline, dimethyl sulfone, 2-methylpropanoic acid, butanoic acid, hexanal, 3-methylbutanoic acid, 2-methylbutanoic acid, 2,4-dimethylbenzaldehyde, 2-phenoxyethanol, and citral (contains both isomers of neral and geranial). Some of these airborne biomolecules were also reported as semiochemicals associated with biological functions of other spiders and insects. The method was also applied to study the airborne biochemicals of Plectreurys tristis, another primitive hunting spider with a poor web, enabling quantitation of the same compounds and demonstrating a difference in signaling molecule concentrations between the two species. This method has potential application in the study of pheromones and biological signaling in other species, which allows for the possibility of utilizing attractant or deterrent functions to limit household populations of harmful species.

The increasing prevalence of products that incorporate engineered nanoparticles (ENPs) has prompted efforts to investigate the potential release, environmental fate, and exposure of the ENPs. However, the investigation of cerium dioxide nanoparticles (CeO2 NPs) in soil has remained limited, owing to the analytical challenge from the soil's complex nature. In this study, this challenge was overcome by applying a novel single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) methodology to detect CeO2 NPs extracted from soil, utilizing tetrasodium pyrophosphate (TSPP) aqueous solution as an extractant. This method is highly sensitive for determining CeO2 NPs in soil, with detection limits of size and concentration of 15 nm and 194 NPs mL-1, respectively. Extraction efficiency was sufficient in the tested TSPP concentration range from 1 mM to 10 mM at a soil-to-extractant ratio 1:100 (g mL-1) for the extraction of CeO2 NPs from the soil spiked with CeO2 NPs. The aging study demonstrated that particle size, size distribution, and particle concentration underwent no significant change in the aged soils for a short period of one month. This study showed an efficient method capable of extracting and accurately determining CeO2 NPs in soil matrices. The method can serve as a useful tool for nanoparticle analysis in routine soil tests and soil research.

The increasing use of engineered nanoparticles (ENPs) in many industries has generated significant research interest regarding their impact on the environment and human health. The major routes of ENPs to enter the human body are inhalation, skin contact, and ingestion. Following ingestion, ENPs have a long contact time in the human stomach. Hence, it is essential to know the fate of the ENPs under gastric conditions. This study aims to investigate the fate of the widely used nanoparticles Ag-NP, Au-NP, CeO2-NP, and ZnO-NP in simulated gastric fluid (SGF) under different conditions through the application of single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS). The resulting analytical methods have size detection limits for Ag-NP, Au-NP, ZnO-NP, and CeO2-NP from 15 to 35 nm, and the particle concentration detection limit is 135 particles/mL. Metal ions corresponding to the ENPs of interest were detected simultaneously with detection limits from 0.02 to 0.1 μg/L. The results showed that ZnO-NPs dissolved completely and rapidly in SGF, whereas Au-NPs and CeO2-NPs showed apparent aggregation and did not dissolve significantly. Both aggregation and dissolution were observed in Ag-NP samples following exposure to SGF. The size distributions and concentrations of ENPs were affected by the original ENP concentration, ENP size, the contact time in SGF, and temperature. This work represents a significant advancement in the understanding of ENP characteristics under gastric conditions.

Traumatic brain injury (TBI) is a serious public health concern for which sensitive and objective diagnostic methods remain lacking. While advances in neuroimaging have improved diagnostic capabilities, the complementary use of molecular biomarkers can provide clinicians with additional insight into the nature and severity of TBI. In this study, a panel of eight metabolites involved in distinct pathophysiological processes related to concussion was quantified using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Specifically, the newly developed method can simultaneously determine urinary concentrations of glutamic acid, homovanillic acid, 5-hydroxyindoleacetic acid, methionine sulfoxide, lactic acid, pyruvic acid, N-acetylaspartic acid, and F2α-isoprostane without intensive sample preparation or preconcentration. The method was systematically validated to assess sensitivity (method detection limits: 1-20 μg/L), accuracy (81-124% spike recoveries in urine), and reproducibility (relative standard deviation: 4-12%). The method was ultimately applied to a small cohort of urine specimens obtained from healthy college student volunteers. The method presented here provides a new technique to facilitate future work aiming to assess the clinical efficacy of these putative biomarkers for noninvasive assessment of TBI.

INTRODUCTION: Determining the biological significance of pteridines in cancer development and progression remains an important step in understanding the altered levels of urinary pteridines seen in certain cancers. Our companion study revealed that several folate-derived pteridines and lumazines correlated with tumorigenicity in an isogenic, progressive breast cancer cell model, providing direct evidence for the tumorigenic origin of pteridines. OBJECTIVES: This study sought to elucidate the pteridine biosynthetic pathway in a progressive breast cancer model via direct pteridine dosing to determine how pteridine metabolism changes with tumorigenicity. METHODS: First, MCF10AT breast cancer cells were dosed individually with 15 pteridines to determine which pteridines were being metabolized and what metabolic products were being produced. Second, pteridines that were significantly metabolized were dosed individually across the progressive breast cancer cell model (MCF10A, MCF10AT, and MCF10ACA1a) to determine the relationship between each metabolic reaction and breast cancer tumorigenicity. RESULTS: Several pteridines were found to have altered metabolism in breast cancer cell lines, including pterin, isoxanthopterin, xanthopterin, sepiapterin, 6-biopterin, lumazine, and 7-hydroxylumazine (p < 0.05). In particular, isoxanthopterin and 6-biopterin concentrations were differentially expressed (p < 0.05) with respect to tumorigenicity following dosing with pterin and sepiapterin, respectively. Finally, the pteridine biosynthetic pathway in breast cancer cells was proposed based on these findings. CONCLUSION: This study, along with its companion study, demonstrates that pteridine metabolism becomes disrupted in breast cancer tumor cells. This work highlights several key metabolic reactions within the pteridine biosynthetic pathway that may be targeted for further investigation and clinical applications.

Many drinking water treatment plants in the U.S. have switched from chlorination to chloramination to lower levels of regulated trihalomethane (THM) and haloacetic acid (HAA) disinfection byproducts (DBPs) in drinking water and meet the current regulations. However, chloramination can also produce other highly toxic/carcinogenic, unregulated DBPs: iodo-acids, iodo-THMs, and N-nitrosodimethylamine (NDMA). In practice, chloramines are generated by the addition of chlorine with ammonia, and plants use varying amounts of free chlorine contact time prior to ammonia addition to effectively kill pathogens and meet DBP regulations. However, iodo-DBPs and nitrosamines are generally not considered in this balancing of free chlorine contact time. The goal of our work was to determine whether an optimal free chlorine contact time could be established in which iodo-DBPs and NDMA could be minimized, while keeping regulated THMs and HAAs below their regulatory limits. The effect of free chlorine contact time was evaluated for the formation of six iodo-trihalomethanes (iodo-THMs), six iodo-acids, and NDMA during the chloramination of drinking water. Ten different free chlorine contact times were examined for two source waters with different dissolved organic carbon (DOC) and bromide/iodide. For the low DOC water at pH 7 and 8, an optimized free chlorine contact time of up to 1 h could control regulated THMs and HAAs, as well as iodo-DBPs and NDMA. For the high DOC water, a free chlorine contact time of 5 min could control iodo-DBPs and NDMA at both pHs, but the regulated DBPs could exceed the regulations at pH 7.

Antibiotic resistance has become a worldwide public health threat due to the rapid evolution and spread of antibiotic-resistant bacteria. CCG-211790 is a novel anti-virulence compound that does not kill bacteria but could ameliorate human diseases by inhibiting expression of virulence factors, thereby applying less selection pressure for antibiotic resistance. However, its potential clinical use is restricted because of its poor aqueous solubility, resulting in formulation challenges. Nanosuspension technology is an effective way to circumvent this problem. Nanosuspensions of CCG-211790 with two different particle sizes, NanoA (315 ± 6 nm) and NanoB (915 ± 24 nm), were prepared using an antisolvent precipitation-ultrasonication method with Tween 80 as the stabilizer. Particle and pharmacokinetics (PK) of CCG-211790 nanosuspensions were characterized. Both NanoA and NanoB demonstrated remarkable increases in dissolution rate compared with the bulk compound. The PK parameters of NanoA were comparable to those of CCG-211790 solution formulation in intravenous or oral administration, suggesting that CCG-211790 nanosuspensions with smaller particle size improved oral bioavailability and drug exposure compared to traditional formulations of drug candidates.

Single-cell analysis is an emerging research area that aims to reveal delicate cellular status and underlying mechanisms by conquering the intercellular heterogeneity. Current single-cell research methods, however, are highly dependent on cell-destructive protocols and cannot sequentially display the progress of cellular events. A recently developed pH nanoprobe in our lab conceptually showed its ability to detect intracellular pH (pH(i)) without cell labeling or disruption. In the present study, we took the cytotoxicity of nanoparticles (NPs) as a typical example of cell heterogeneity, to testify the practicality of the pH nanoprobe in interpreting cell status. Three types of NPs (CeO(2), TiO(2), and SiO(2)) were employed to generate varied toxic effects. Results showed that the traditional assays - including cell viability, intracellular ROS generation, and mitochondrial inner membrane depolarization - not only failed to report the nanotoxicity accurately and timely, but also drew confusing or misleading conclusions. The pH nanoprobe revealed explicit pH(i) changes induced by the NPs, which corresponded well with the cell damages found by the transmission electron microscopic (TEM) imaging. Besides, our results unveiled an unexpectedly devastating effect of SiO(2) NPs on cells during the early stage NP-cell interaction. The developed novel pH nanoprobe demonstrated a rapid sensing capability at single-cell resolution with minimum invasiveness. Therefore, it may become a promising alternative for a wide range of applications in areas such as single-cell research and precision medicine.

Accurate determination of the drug-to-antibody ratio (DAR) of interchain cysteine-linked antibody-drug conjugates (ADCs) is challenging. High-resolution mass spectrometry (HRMS) analysis of the ADCs at the intact or subunit level provides a feasible way to measure the DAR. However, the measured DAR is usually lower than the true DAR because of the variation in ionization efficiency between different DAR species. In this work, we developed a novel standard-free HRMS method involving isotope-labeled payload conjugation, protease digestion, and liquid chromatography-HRMS (LC-HRMS) analysis for accurate determination of the DAR of the interchain cysteine-linked ADCs with cleavable or non-cleavable linkers. Isotope-labeled payload conjugations eliminated the structural and chemical differences between different DAR species and ensured that the drugs or payload-containing peptides could be separated from each other in the mass spectrometer. A papain digestion strategy for ADCs with cleavable linkers showed a DAR of 3.79, with a relative standard deviation (RSD) of 0.48 (n = 3). Similarly, the trypsin and chymotrypsin digestion strategy that is applicable to ADCs with non-cleavable linkers showed a DAR of 3.77 and an RSD of 0.86 (n = 3). The DAR determined by this method was consistent with the DAR of the ADCs that was measured by the UV/Vis method. This method will be very useful to researchers working in the field of ADC discovery and development. Graphical abstract.

Effluent from wastewater treatment plants contains a wide variety of engineered nanoparticles (ENPs) released from different sources. Although single type ENPs have been studied extensively with respect to their environmental impact, ENPs in mixed forms have not been investigated much at environmentally relevant concentrations. This study was designed to test the effect of mixed ENPs at three combinations and concentrations on an aquatic bacterial community. After mixing artificial treated wastewater with river water and exposing the microbial community to ENPs for three days, the ENPs were characterized by SP-ICP-MS. Results from this study showed that: 1) the size distribution of Ti and Zn at the beginning and end of the experiment did not vary much among all tested conditions. For Ag, the most frequent size increased more than 2-fold when the highest Ag ENPs were added; 2) particle concentrations of ENPs generally correlated positively with added concentrations; 3) dissolved Zn and Ag increased significantly as a result of spike; and 4) the bacterial community structure was shifted significantly as a consequence of ENPs’ addition. With the dominant population being suppressed, the community exposed to ENPs became more diverse and even. Surprisingly, further increase of the doses of the three ENPs did not bring significant change to the microbial community. These results revealed that ENPs could bring significant impacts to prokaryotes even at low concentrations. But these impacts do not necessarily correlate positively with doses.

Interchain cysteine linked antibody-drug conjugates (ADCs) are emerging therapeutic products that antagonize cancers. The toxic payloads are selectively linked to the interchain cysteines and generate heterogeneous mixtures of positional isomers. These positional isomers might contribute differently to the therapeutic efficacy because of the variation in conjugation stability, and thus they need to be well characterized. However, the characterization of the positional isomers of interchain cysteine linked ADCs is very challenging, mainly because of the high similarity between those isomers. In this research, we developed a novel mass spectrometry method for the characterization of positional isomers of interchain cysteine linked ADCs. The subunit analysis and the bottom-up analysis provided abundant information about the drug numbers and drug linking positions on each chain. Because the method can provide accurate data on drug linking numbers and positions on each chain, it will be very useful for researchers in cancer drug development and cancer treatment.

Single cell-inductively coupled plasma-mass spectrometry (SC-ICP-MS) is an emerging technology. In this work, we have developed a novel SC-ICP-MS method to quantify metal ions in individual cells of a toxic cyanobacterial species, Microcystis aeruginosa (M. aeruginosa), without complicated post-dosing sample preparation, and applied this method to study the treatment effectiveness of copper-based algaecides (cupric sulfate and EarthTec®) on the toxic algae M. aeruginosa. The developed SC-ICP-MS method uses new intrinsic metal element magnesium to determine real transport efficiency and cell concentration. The cell viability and microcystin-LR release by algaecide treatment were studied by flow cytometry and ultra-fast liquid chromatography-tandem mass spectrometry, respectively. The results showed that this novel method was very rapid, highly sensitive (detection limits of intracellular copper and magnesium were 65 ag/cell and 98 ag/cell, respectively), and reproducible (relative standard deviation within 12%). The algaecide effectiveness study further demonstrated that copper in the forms of cupric sulfate and copper-based algaecide EarthTec® successfully diminished M. aeruginosa populations. The higher the copper concentration used to treat the cells, the faster the speeds of copper uptake and cell lysis in the copper concentrations ranged from 0 to 200 μg/L of copper-based algaecide. The cells exhibit obvious heterogeneity in copper uptake. The result suggests that M. aeruginosa cells uptake and cumulate copper followed by cellular lysis and microcystin-LR release. These novel results indicated that though the copper-based algaecides could control this type of harmful algal bloom, further treatment to remove the released algal toxin from the treated water would be needed. Graphical abstract Electronic supplementary material The online version of this article (10.1007/s00216-019-01933-9) contains supplementary material, which is available to authorized users.

Emerging and fugitive contaminants (EFCs) can be introduced into the food chain through plants, particularly crop plants, and have threatened food safety and human health. The method for determination of volatile EFCs in plant tissues remains challenging. A new rapid, simple, precise, and accurate freeze-thaw-equilibration followed by head space (HS)-solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) analytical method was developed in this study for high-throughput analysis of 1,4-dioxane and 1,2,3-trichloropropane (TCP) in tissues of three representative crop plants, corn, wheat, and tomato. The samples were treated by a freeze-thaw procedure, then equilibrated in a saturated sodium sulfate solution, and analyzed by HS-SPME-GC-MS method. Method detection limits ranged from 0.6 to 16 ng/g. The calibration showed good linearity (R2 > 0.9). Recoveries of spiked analytes in the three plant species ranged from 82.69 to 106.3%. The ability of plant uptake of the compounds from soil has been investigated. As demonstrated in this study, this method is used to measure the concentrations of volatile contaminants in the stems of crop plants. This method should also be applicable for other plant tissues and therefore will contribute significantly to the sight of EFC transport in plants and to assess the potential risks EFCs pose to food safety and human health.

Oxidative stress is reported to be part of the pathology of many ocular diseases. For the diagnosis of ocular diseases, tear fluid has unique advantages. Although numerous analytical methods exist for the measurement of different types of biomolecules in tear fluid, few have been reported for comprehensive understanding of oxidative stress-related thiol redox signaling. In this study, a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed to determine a panel of twelve metabolites that systematically covered several thiol metabolic pathways. With optimization of MS/MS parameters and HPLC mobile phases, this method was sensitive (LOQ as low as 0.01 ng/mL), accurate (80–125% spike recovery) and precise (

The increasing prevalence of products that incorporate engineered nanoparticles (ENPs) has prompted efforts to investigate the potential release, environmental fate, and exposure of the ENPs. However, the investigation of cerium dioxide nanoparticles (CeO(2) NPs) in soil has remained limited, owing to the analytical challenge from the soil’s complex nature. In this study, this challenge was overcome by applying a novel single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) methodology to detect CeO(2) NPs extracted from soil, utilizing tetrasodium pyrophosphate (TSPP) aqueous solution as an extractant. This method is highly sensitive for determining CeO(2) NPs in soil, with detection limits of size and concentration of 15 nm and 194 NPs mL(−1), respectively. Extraction efficiency was sufficient in the tested TSPP concentration range from 1 mM to 10 mM at a soil-to-extractant ratio 1:100 (g mL(−1)) for the extraction of CeO(2) NPs from the soil spiked with CeO(2) NPs. The aging study demonstrated that particle size, size distribution, and particle concentration underwent no significant change in the aged soils for a short period of one month. This study showed an efficient method capable of extracting and accurately determining CeO(2) NPs in soil matrices. The method can serve as a useful tool for nanoparticle analysis in routine soil tests and soil research.

The emergence of antibiotic resistance over the past several decades has given urgency to new antibacterial strategies that apply less selective pressure. A new class of anti-virulence compounds were developed that are active against methicillin-resistant Staphylococcus aureus (MRSA), by inhibiting bacterial virulence without hindering their growth to reduce the selective pressure for resistance development. One of the compounds CCG-211790 has demonstrated potent anti-biofilm activity against MRSA. This new class of anti-virulence compounds inhibited the gene expression of virulence factors involved in biofilm formation and disrupted the biofilm structures. In this study, the physicochemical properties of CCG-211790, including morphology, solubility in pure water or in water containing sodium dodecyl sulfate, solubility in organic solvents, and stability with respect to pH were investigated for the first time. Furthermore, a topical formulation was developed to enhance the therapeutic potential of the compound. The formulation demonstrated acceptable properties for drug release, viscosity, pH, cosmetic elegance and stability of over nine months.

Uptake of seven organic contaminants including bisphenol A, estriol, 2,4-dinitrotoluene, N,N-diethyl-meta-toluamide (DEET), carbamazepine, acetaminophen, and lincomycin by tomato (Solanum lycopersicum L.), corn (Zea mays L.), and wheat (Triticum aestivum L.) was measured. The plants were grown in a growth chamber under recommended conditions and dosed by these chemicals for 19 days. The plant samples (stem transpiration stream) and solution in the exposure media were taken to measure transpiration stream concentration factor (TSCF). The plant samples were analyzed by a freeze-thaw centrifugation technique followed by high performance liquid chromatography-tandem mass spectrometry detection. Measured average TSCF values were used to test a neural network (NN) model previously developed for predicting plant uptake based on physicochemical properties. The results indicated that moderately hydrophobic compounds including carbamazepine and lincomycin have average TSCF values of 0.43 and 0.79, respectively. The average uptake of DEET, estriol, acetaminophen, and bisphenol A was also measured as 0.34, 0.29, 0.22, and 0.1, respectively. The 2,4-dinitrotoluene was not detected in the stem transpiration stream and it was shown to degrade in the root zone. Based on these results together with plant physiology measurements, we concluded that physicochemical properties of the chemicals did predict uptake, however, the role of other factors should be considered in the prediction of TSCF. While NN model could predict TSCF based on physicochemical properties with acceptable accuracies (mean squared error less than 0.25), the results for 2,4-dinitrotoluene and other compounds confirm the needs for considering other parameters related to both chemicals (stability) and plant species (role of lipids, lignin, and cellulose).

The increasing use of engineered nanoparticles (ENPs) in many industries has generated significant research interest regarding their impact on the environment and human health. The major routes of ENPs to enter the human body are inhalation, skin contact, and ingestion. Following ingestion, ENPs have a long contact time in the human stomach. Hence, it is essential to know the fate of the ENPs under gastric conditions. This study aims to investigate the fate of the widely used nanoparticles Ag-NP, Au-NP, CeO(2)-NP, and ZnO-NP in simulated gastric fluid (SGF) under different conditions through the application of single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS). The resulting analytical methods have size detection limits for Ag-NP, Au-NP, ZnO-NP, and CeO(2)-NP from 15 to 35 nm, and the particle concentration detection limit is 135 particles/mL. Metal ions corresponding to the ENPs of interest were detected simultaneously with detection limits from 0.02 to 0.1 μg/L. The results showed that ZnO-NPs dissolved completely and rapidly in SGF, whereas Au-NPs and CeO(2)-NPs showed apparent aggregation and did not dissolve significantly. Both aggregation and dissolution were observed in Ag-NP samples following exposure to SGF. The size distributions and concentrations of ENPs were affected by the original ENP concentration, ENP size, the contact time in SGF, and temperature. This work represents a significant advancement in the understanding of ENP characteristics under gastric conditions.

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.

Nanomaterials (NM) are incorporated into polymers to enhance their properties. However, there are a limited number of studies on the aging of these nanocomposites and the resulting potential release of NM. To characterize NM at critical points in their life cycles, polypropylene (PP) and multiwall carbon nanotube filled PP (PP-MWCNT) plates with different thicknesses (from 0.25 mm to 2 mm) underwent accelerated weathering in a chamber that simulates solar irradiation and rainfall. The physicochemical changes of the plates depended on the radiation exposure, the plate thickness, and the presence of CNT fillers. Photodegradation increased with aging time, making the exposed surface more hydrophilic, decreasing the surface hardness and creating surface stress-cracks. Aged surface and cross-section showed crazing due to the polymer bond scission and the formation of carbonyls. The degradation was higher near the UV-exposed surface as the intensity of the radiation and oxygen diffusion decreased with increasing depth of the plates, resulting in an oxidation layer directly proportional to oxygen diffusion. Thus, sample thickness determines the kinetics of the degradation reaction and the transport of reactive species. Plastic fragments, which are less than 1 mm, and free CNTs were released from weathered MWCNT-PP. The concentrations of released NM that were estimated using ICP-MS, increased with prolonged aging time. Various toxicity tests, including reactive oxygen species generation and cell activity/viability, were performed on the released CNTs. The toxicity of the released fragments and CNTs to A594 adenocarcinomic human alveolar basal epithelial cells was observed. The released polymer fragments and CNTs did not show significant toxicity under the experimental conditions in this study. This study will help manufacturers, users of consumer products with nanocomposites and policymakers in the development of testing guidelines, predictive models, and risk assessments and risk based-formulations of NM exposure.

Intracellular pH plays critical roles in cell and tissue functions during processes such as metabolism, proliferation, apoptosis, ion transportation, endocytosis, muscle contraction and so on. It is thus an important biomarker that can readily be used to monitor the physiological status of a cell. Thus, disrupted intracellular pH may serve as an early indicator of cell dysfunction and deterioration. Various methods have been developed to detect cellular pH, such as pH-sensitive labeling reagents with fluorescent or Raman signals. However, excessive cellular uptake of these reagents will not only disrupt cell viability but also compromise effective long-term monitoring. Here, we present a novel fiber-optic fluorescent nanoprobe with a high spatial resolution for label-free, subcellular pH sensing. The probe has a fast response time (~20 seconds) with minimum invasiveness and excellent pH resolution (0.02 pH units) within a biologically relevant pH environment ranging from 6.17 to 8.11. Its applicability was demonstrated on cultured A549 lung cancer cells, and its efficacy was further testified in two typical cytotoxic cases using carbonylcyanide 3-chlorophenyl hydrazine, titanium dioxide, and nanoparticles. The probe can readily detect the pH variations among cells under toxin/nanoparticles administration, enabling direct monitoring of the early onset of physiological or pathological events with high spatiotemporal resolution. This platform has excellent promise as a minimum invasive diagnostic tool for pH-related cellular mechanism studies, such as inflammation, cytotoxicity, drug resistance, carcinogenesis, stem cell differentiation and so on.

Companies in the United States need to mine billions of tons of raw natural aggregate each year. At the same time, billions of scrap tires are stockpiled every year. As a result, replacing the natural aggregate with recycled aggregate is beneficial to the construction industry and the environment. This paper is part of a comprehensive project that developed, and field implemented, a new eco-friendly rubberized chip seal where the mineral aggregate in chip seal is partially or totally replaced with crumb rubber made of recycled tires. This paper presents an extensive study of the environmental impact of using rubber aggregate in chip seal pavement in terms of leaching under different pH conditions, including simulated acid rain. The results are compared with those of conventional chip seal. Leaching from the constituents of chip seal, that is, rubber aggregate and emulsion, was investigated. Two types of rubber and two types of asphalt emulsions were studied. The leaching performance of rubberized chip seal was also investigated. This study revealed that the toxic heavy metals leached from the rubberized chip seal, for pH ranging from 4 to 10, were below that of the EPA drinking water standards. In addition, a significant reduction of heavy metal leaching was recorded when rubber was used with emulsion in the form of chip seal pavement under different pH conditions. Finally, the metal leaching in all types of samples (including rubber, asphalt emulsion, and chip seal) decreased with the increase in pH value.

To investigate effects of engineered nanoparticles (ENPs) at environmentally relevant concentrations to aquatic microbial communities, TiO2 at 700 µg/L and ZnO at 70 µg/L were spiked to river water samples either separately or combined. Compared to controls where no ENPs were added, the addition of TiO2 ENPs alone at the tested concentration had no statistically significant effect on both the bacterial and eukaryotic communities. The presence of added ENPs: ZnO or ZnO + TiO2 led to significant shift of the microbial community structure and genus distribution. This shift was more obvious for the bacteria than the eukaryotes. Based on results from single particle - inductively coupled plasma - mass spectrometry (SP-ICP-MS), all ENPs aggregated rapidly in water and resulted in much larger particles sizes than the original counterparts. "Dissolved" (including particles smaller than the size detection limits and dissolved ions) concentrations of Ti and Zn increased, too in treatment groups vs. the controls.

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.

Even though the plant uptake of cerium oxide nanoparticles (CeO2 NPs) has been reported, the mechanisms remain unknown. This study aimed to provide new insights into CeO2 NPs plant uptake through two objectives: (1) to investigate whether CeO2 NPs dissolute before their plant uptake and (2) to determine the in-planta speciation of Ce. Bench scale experiments were conducted by growing radish in solutions containing 10 mg elemental Ce/L of bulk CeO2 particles, CeO2 NPs or ionic Ce. Transmission electron microscope and inductively coupled plasma-mass spectrometry (ICP-MS) analysis suggested that one pathway for CeO2 NPs uptake was through direct uptake of intact CeO2 NPs. More importantly, our results confirmed that part of the particulate CeO2 was transformed into ionic Ce on the root surface before they were taken up by plants. Ionic Ce uptake and transport was a primary mechanism for Ce accumulation in plant shoots. This study further demonstrated that enhanced CeO2 dissolution on root surface was due to the organic acids with lower molecular weight (e.g. succinic acid) in radish root exudates. Large particles composed of high contents of P and Ce were detected in radish roots treated only with ionic Ce, suggesting the formation of CePO4 particles. In summary, the results indicated that CeO2 NPs was taken up by radish as both intact nanoparticles and dissolved ions. Inside plant tissues, Ce is present as a cocktail of CeO2 NPs, dissolved Ce and Ce salt (e.g. CePO4) and the specific combination of Ce species is tissue dependent.

Emerging and fugitive contaminants (EFCs) released to our biosphere have caused a legacy and continuing threat to human and ecological health, contaminating air, water, and soil. Polluted media are closely linked to food security through plants, especially agricultural crops. However, measuring EFCs in plant tissues remains difficult, and high-throughput screening is a greater challenge. A novel rapid freeze-thaw/centrifugation extraction followed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis was developed for high-throughput quantification of 11 EFCs with diverse chemical properties, including estriol, codeine, oxazepam, 2,4-dinitrotoluene, 1,3,5-trinitroperhydro-1,3,5-triazine, bisphenol A, triclosan, caffeine, carbamazepine, lincomycin, and DEET, in three representative crops, corn, tomato, and wheat. The internal aqueous solution, i.e., sap, is liberated via a freeze/thaw cycle, and separated from macromolecules utilizing molecular weight cutoff membrane centrifugal filtration. Detection limits ranged from 0.01 μg L

To develop and verify the Psychosomatic Symptom Scale (PSSS) among psychosomatic patients and the cut-off value of PSSS in distinguishing psychosomatic patients from health controls.The PSSS was drafted by an expert workgroup. 996 patients and 366 controls from 14 general hospitals in China were recruited to complete PSSS, Patient Health Questionnaire-15 (PHQ-15) and Symptom Checklist-90 (SCL-90). Student's t-test, Kruskal-Wallis test, Cronbach's α, Spearman's correlation, and confirmatory factor analysis (CFA) were used to verify the PSSS. Receiver operating characteristic (ROC) analyses were used to determine the cut-off value.Cronbach α of PSSS was 0.907. The PSSS was significantly correlated with SCL-90 somatization subscale (r = 0.682, P 0.001) and PHQ-15 (r = 0.724, P 0.001). CFA supported the theoretical two-factor structure of the PSSS, with comparative fit index (CFI) = 0.979, Tucker-Lewis index (TLI) = 0.977, root mean square error of approximation (RMSEA) = 0.039 (90% CI: 0.035-0.042), and standardized root mean residual (SRMR) = 0.054. As the sum score of PSSS was significantly higher in female, cut-off values were determined as 11 in females and 10 in males respectively.The PSSS is a reliable and valid instrument for measuring psychosomatic symptoms.

Nanomaterials (NM) are incorporated into polymers to enhance their properties. However, there are a limited number of studies on the aging of these nanocomposites and the resulting potential release of NM. To characterize NM at critical points in their life cycles, polypropylene (PP) and multiwall carbon nanotube filled PP (PP-MWCNT) plates with different thicknesses (from 0.25 mm to 2 mm) underwent accelerated weathering in a chamber that simulates solar irradiation and rainfall. The physicochemical changes of the plates depended on the radiation exposure, the plate thickness, and the presence of CNT fillers. Photodegradation increased with aging time, making the exposed surface more hydrophilic, decreasing the surface hardness and creating surface stress-cracks. Aged surface and cross-section showed crazing due to the polymer bond scission and the formation of carbonyls. The degradation was higher near the UV-exposed surface as the intensity of the radiation and oxygen diffusion decreased with increasing depth of the plates, resulting in an oxidation layer directly proportional to oxygen diffusion. Thus, sample thickness determines the kinetics of the degradation reaction and the transport of reactive species. Plastic fragments, which are less than 1 mm, and free CNTs were released from weathered MWCNT-PP. The concentrations of released NM that were estimated using ICP-MS, increased with prolonged aging time. Various toxicity tests, including reactive oxygen species generation and cell activity/viability, were performed on the released CNTs. The toxicity of the released fragments and CNTs to A594 adenocarcinomic human alveolar basal epithelial cells was observed. The released polymer fragments and CNTs did not show significant toxicity under the experimental conditions in this study. This study will help manufacturers, users of consumer products with nanocomposites and policymakers in the development of testing guidelines, predictive models, and risk assessments and risk based-formulations of NM exposure.

Effluent from wastewater treatment plants contains a wide variety of engineered nanoparticles (ENPs) released from different sources. Although single type ENPs have been studied extensively with respect to their environmental impact, ENPs in mixed forms have not been investigated much at environmentally relevant concentrations. This study was designed to test the effect of mixed ENPs at three combinations and concentrations on an aquatic bacterial community. After mixing artificial treated wastewater with river water and exposing the microbial community to ENPs for three days, the ENPs were characterized by SP-ICP-MS. Results from this study showed that: 1) the size distribution of Ti and Zn at the beginning and end of the experiment did not vary much among all tested conditions. For Ag, the most frequent size increased more than 2-fold when the highest Ag ENPs were added; 2) particle concentrations of ENPs generally correlated positively with added concentrations; 3) dissolved Zn and Ag increased significantly as a result of spike; and 4) the bacterial community structure was shifted significantly as a consequence of ENPs' addition. With the dominant population being suppressed, the community exposed to ENPs became more diverse and even. Surprisingly, further increase of the doses of the three ENPs did not bring significant change to the microbial community. These results revealed that ENPs could bring significant impacts to prokaryotes even at low concentrations. But these impacts do not necessarily correlate positively with doses.

In this study, we proposed a new nonlinear partial least squares (NPLS) method using time difference (TD) method for modeling chemical and environmental processes. The TD-NPLS method embeds the TD method into the NPLS modeling, where a prior knowledge related to key process information can be utilized. The NPLS can model the nonlinear inner relationships in a reduced data dimension and the TD method captures the gradual changes, which results in the deterioration of the predictive accuracy. The TD-NPLS method is aimed at achieving a high predictive accuracy by simultaneously capturing the characteristics of nonlinearity and dynamics in a single modeling framework. The results in three case studies, one simulated case and two industrial environmental cases showed that the TD-NPLS method absolutely has a higher predictive accuracy in modeling nonlinear and auto-correlated processes than the linear PLS, NPLS, and TD-LPLS models.

A novel material was prepared by depositing ultrathin TiO 2 films on nanoporous micron-sized silica gel particles by atomic layer deposition (ALD). Silica gel particles were coated with 20 and 40 cycles of TiO 2 films by ALD. Half samples were heated at 500 °C to change the crystal structure of TiO 2 . Their adsorption ability for a mixture of 19 trace elements of heavy metals and other toxic elements, including As(V), Se(IV), Be(II), Al(III), V(V), Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Ba(II), Tl(I), Sb(III), Cd(II), Ag(I), Sr(II), Mo(VI), and Pb(II), from aqueous solutions was investigated. The removal efficiencies of As(V), Se(IV), V(V), Mo(VI), and Pb(II) were higher than 75% simultaneously in the mixed solution at pH 3 for 20 and 40 cycles of TiO 2 coated silica gel particles without heat treatment. In contrast, the uncoated silica gel particles did not adsorb any ions under this pH condition. At pH 5, the 20 cycles of TiO 2 coated samples without heat treatment removed 95% As(V), 95% Se(IV), 86% V(V), 94% Mo(VI), 60% Pb(II), 40% Sb(III), 73% Ag(I), 72% Cu(II), and 49% Ba(II) simultaneously. Before heat treatment, the TiO 2 coated samples showed better adsorption performance than the samples with heat treatment due to the fact that the TiO 2 surface area decreased and thereby the amount of adsorption sites reduced after heat treatment. The micron-sized adsorbent particles were separated easily from water due to their large particle size, making it practically suitable for trace contaminant remediation in water.

A simple, sensitive, and selective solid phase extraction – ultra-fast liquid chromatography – tandem mass spectrometry (SPE-UFLC-MS/MS) method was developed and applied for the analysis of selected important pharmaceutical compounds in source and finished drinking waters. The method detected the following six pharmaceuticals, cotinine, cephapirin, ciprofloxacin, enrofloxacein, azithromycin, and diphenhydramine, at sub-μg/L level in multiple water matrices after pre-concentration by SPE. Cotinine-d3 and 13C315 N-Ciprofloxacin were used as internal standards for accurate quantitation. This method was validated through spike recoveries (67–129%), reproducibility (RSD: 2.3–15.7%), and method detection limits (MDLs: 2–5 ng/L). The method was used to test for occurrence of these pharmaceuticals in source and drinking waters from 13 Missouri water treatment facilities in four different seasons. In general, higher detection frequency and concentrations of pharmaceuticals were observed in colder months du...

The fate and impact of cerium oxide nanoparticles (CeO2NPs) on soil-grown plants have been intensively studied. However, all previous studies were performed in freshly prepared soils, without considering the temporal changes of the properties of CeO2NPs in the environment. A growing body of evidence suggests that the properties of CeO2NPs will change with aging, and therefore, it is essential to understand how the aging process affects the fate and bioavailability of CeO2NPs in the environment. In this study, the effects of aging on the fractionation of CeO2NPs in a silty loam soil and their bioavailability to radish were investigated. The results indicated that aging for 7 months did not affect the fractionation of CeO2NPs in soil. However, the aging process significantly increased the concentration of Ce3+ in soil. The soil with aged CeO2NPs contained a 40.5% higher concentration of Ce3+ than soil with fresh CeO2NPs. The aging process also resulted in a significantly higher Ce concentration in the radis...

Haloacetic acids (HAAs), which include chloroacetic acids, bromoacetic acids, and emerging iodoacetic acids, are toxic water disinfection byproducts. General screening methodology is lacking for simultaneously monitoring chloro-, bromo-, and iodoacetic acids. In this study, a rapid and sensitive high-performance ion chromatography-tandem mass spectrometry method for simultaneous determination of chloro-, bromo-, and iodo- acetic acids and related halogenated contaminants including bromate, bromide, iodate, and iodide was developed to directly analyze water samples after filtration, eliminating the need for preconcentration, and chemical derivatization. The resulting method was validated in both untreated and treated water matrices including tap water, bottled water, swimming pool water, and both source water and drinking water from a drinking water treatment facility to demonstrate application potential. Satisfactory accuracies and precisions were obtained for all types of tested samples. The detection limits of this newly developed method were lower or comparable with similar techniques without the need for extensive sample treatment requirement and it includes all HAAs and other halogenated compounds. This provides a powerful methodology to water facilities for routine water quality monitoring and related water research, especially for the emerging iodoacetic acids. Graphical abstract High performance ion chromatography-tandem mass spectrometry method for detection of haloacetic acids in water.

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.

One of the most direct means for human exposure to nanoparticles (NPs) released into the environment is drinking water. Therefore, it is critical to understand the occurrence and fate of NPs in drinking water systems. The objectives of this study were to develop rapid and reliable analytical methods and apply them to investigate the fate and transportation of NPs during drinking water treatments. Rapid single particle ICP-MS (SP-ICP-MS) methods were developed to characterize and quantify titanium-containing, titanium dioxide, silver, and gold NP concentration, size, size distribution, and dissolved metal element concentration in surface water and treated drinking water. The effectiveness of conventional drinking water treatments (including lime softening, alum coagulation, filtration, and disinfection) to remove NPs from surface water was evaluated using six-gang stirrer jar test simulations. The selected NPs were nearly completely (97 ± 3%) removed after lime softening and alum coagulation/activated carbon adsorption treatments. Additionally, source and drinking waters from three large drinking water treatment facilities utilizing similar treatments with the simulation test were collected and analyzed by the SP-ICP-MS methods. Ti-containing particles and dissolved Ti were present in the river water samples, but Ag and Au were not present. Treatments used at each drinking water treatment facility effectively removed over 93% of the Ti-containing particles and dissolved Ti from the source water.