Aqueous Concentrations Research Articles

Effects of size and composition of bitumen drops on intra-oil diffusion and dissolution of hydrocarbon solvents in froth treatment tailings ponds

The rate of mass transfer of lower molecular weight hydrocarbons (naphtha) from bitumen drops in mature fine tailings of oil sand tailings ponds (OSTPs) may control their bioavailability and the associated rate of GHG production. Experiments were conducted using bitumen drops spiked with o-xylene and 1-methylnaphthalene to determine the mass transfer rate of these naphtha components from bitumen drops. The results were compared to simulations using a multi-component numerical model that accounted for transport in the drop and across the oil-water interface. The results demonstrate rate-limited mass transfer, with aqueous concentrations after 60 days of dissolution that were different than those in equilibrium with the initial drop composition (less for o-xylene and greater for 1-methylnaphthalene). The simulations suggest that mole fractions were unchanged at the center of the drop, resulting in concentration gradients out to the oil-water interface. Numerical simulations conducted using different drop sizes and bitumen viscosities also suggest the potential for persistent naphtha dissolution, where the time required to deplete 80% of the o-xylene and 1-methylnaphthalene mass from an oil drop was estimated to be on the order of months to years for mm-sized drops, and years to decades for cm-sized drops assuming instantaneous biodegradation in the aqueous phase surrounding the bitumen.

Detection and intelligent optimization of blood glucose signals based on MXene-assisted sensors

Two-dimensional materials exhibit unique properties that make them ideal for electronic sensing applications, particularly in the field of biosensors. In this study, a Ti3C2Tx MXene/graphene composite was investigated for its potential use in non-invasive blood glucose detection. The strong electrostatic interaction between MXene and graphene nanosheets effectively reduces the self-stacking of both components, resulting in the formation of a porous interlayer structure with enlarged interlayer spacing. This unique structure creates an efficient nanoscale transport channel, which increases the number of active sites and shortens ion diffusion paths. Consequently, the electrochemical properties of the composite membrane are enhanced, making it a promising candidate for sensing element applications. As the human blood glucose level is primarily determined by the glucose concentration in the blood, the concentration of glucose solution serves as the foundation for noninvasive blood glucose concentration detection. In this work, a prediction model was established using the partial least squares fitting method to correlate the electrochemical fingerprinting data with the glucose aqueous solution concentration, and the reliability of the model was verified. To address the limitations of the partial least squares method, which lacks nonlinear fitting capabilities, an RBF (radial basis function) network model was employed. Finally, a genetic algorithm was utilized to perform global optimization of the training parameters of the RBF network, and the quantitative relationship between the NIR spectral data and glucose concentration was validated. The findings of this study provide a theoretical basis for the development of equipment and the improvement of measurement accuracy in the field of human noninvasive glucose detection.

CLINICAL CHARACTERIZATION OF AQUEOUS AND VITREOUS RETINOL-BINDING PROTEIN 3 CONCENTRATIONS IN RELATION TO DIABETIC RETINOPATHY SEVERITY, RETINAL STRUCTURES, AND SYSTEMIC COMPLICATIONS.

To evaluate Retinol-Binding Protein 3 (RBP3) from photoreceptors in aqueous and its association with vitreous concentrations, diabetic retinopathy (DR) severity, retinal layer thickness, and clinical characteristics in people with diabetes. RBP3 concentration was measured by custom-developed enzyme-linked immunosorbent assay in aqueous and correlated with vitreous concentrations in patients from the 50-Year Medalist study and Beetham Eye Institute at Joslin Diabetes Center. Aqueous RBP3 concentration (N = 131) was elevated in eyes with no to mild DR (mean ± SD 0.7 nM ± 0.2) and decreased in eyes with moderate to severe DR (0.65 nM ± 0.3) and proliferative DR (0.5 nM ± 0.2, P < 0.001) compared to eyes without diabetes. Aqueous and vitreous RBP3 concentrations correlated with each other (r = 0.34, P = 0.001) and between fellow eyes (P < 0.0001). History of retinal surgery did not affect aqueous RBP3 concentrations, but cataract surgery affected both vitreous and aqueous levels. Elevated aqueous RBP3 concentration associated with increased thickness of the outer nuclear layer (P = 0.004) and correlated with hemoglobin A1c, whereas vitreous RBP3 concentrations correlated with diabetic systemic complications. These findings suggest that aqueous RBP3 concentration may be an important endogenous clinical retinal protective factor, a biomarker for DR severity, and a promising VEGF-independent clinical intervention target in DR.

Dynamics of micro and macronutrients in a hydroponic nutrient film technique system under lettuce cultivation

While hydroponics is considered an efficient vegetable production system, there is a compelling need to investigate the efficiency of the current generic nutrient dosing recommendation primarily based on electrical conductivity (EC) measurements. Such information is critical to fine-tune and optimize the current hydroponic management practices for improved nutrient uptake efficiency. This study investigated the dynamics of some micro and macronutrients (N, P, Ca, Mg, K, Fe, and Mn) in a recirculating nutrient film technique (NFT) hydroponic system under lettuce cultivation. The research was conducted in an indoor controlled environment growth chamber with lettuce grown in different EC levels (1.2 and 1.6 dS m−1). Each treatment had four hydroponic cultivation units, each one with 24 plants. Nutrient solution and tissue samples were collected two to three times per week. Nutrient dynamics, including nutrient uptake efficiencies and environmental losses, were calculated using a mass balance approach. The effects of EC level on fresh and dry lettuce biomass and nutrient uptake were insignificant. Observed variations in nutrient solution composition during lettuce cultivation included the almost complete removal of ammonia nitrogen, nitrate decreases towards the end of the experiment, consistent increases in aqueous Ca concentration, and corresponding decreases in K and Mn. Average N losses ranged between 27 and 40 %, presumably through denitrification, while 10–14 % of N was assimilated into the plant biomass. The remaining N in the recirculating nutrient solution was estimated to be between 50 and 59 %. The average P loss was 11–35 %, likely due to precipitation, while 52–77 % remained in the nutrient solution. Nutrient uptake efficiencies averaged 19–31 % K, 12–21 % P, 9–16 % Mn, 4–6 % Ca, 3–4 % Mg, and 2–4 % Fe. These results suggest that elevated nutrient concentrations in recirculating nutrient solutions led to losses and underutilization. Findings from this study provide a comprehensive dataset critical to improving hydroponic nutrient management beyond N and P. Hydroponic nutrient management should target providing essential nutrients needed by plants at the correct proportions considering the plant growth stage.

An in vitro study to determine the impact of lipid emulsion on partitioning of a broad spectrum of drugs associated with overdose

BackgroundIntravenous lipid emulsion is recognised as a therapy for rescue in cases of local anaesthetic toxicity, but its use in reversing overdose or toxicity related to other drugs remains the subject of debate. This in vitro study sought to expand our understanding of the importance of partitioning in determining the impact of intravenous lipid emulsion on aqueous free drug concentrations. MethodsTwenty-seven drugs and associated metabolites were screened for the ability of intravenous lipid emulsion to reduce the amount of free drug in the aqueous phase, using specialised cassettes designed for this purpose. The relative amount of drug equilibrating across the membrane from plasma to phosphate-buffered saline was measured, using liquid chromatography–mass spectrometry, at a 6 h timepoint in plasma samples treated with intravenous lipid emulsion and paired, untreated controls. ResultsThe data obtained were plotted against measures of partition (LogP and cLogD7.4) and with log-transformed non-protein bound drug. There were significant inverse correlations between the capacity for intravenous lipid emulsion to reduce drug detected in the phosphate-buffered saline compartment and LogP and cLogD7.4, and a direct association with log [non-protein-bound drug]. However, a number of drugs showed substantial variance between different plasma samples. ConclusionsModulation of free drug in the aqueous compartment is broadly predictable by the partition coefficient, although ramipril was identified to be an outlier in this regard. Further mechanistic and clinical exploration is merited to establish a standardised protocol for lipid emulsion therapy.

A fluorescent functionalized PET fabric with dual-response to aqueous copper and pH

A fluorescent functional PET fabric for effective aqueous copper detection was developed. Eu(TTA)3·2H2O complex was prepared by the solvothermal method and subsequently PET fluorescent nonwoven fabrics were prepared by coordinating the complexes with PET nonwoven fabrics grafted with acrylic acid.The chemical structure and microscopic morphology of the fluorescent nonwovens were analyzed, and the effects of different experimental conditions (grafting rate, reaction time, and fluorescent complex concentration) on the fluorescence properties of the materials were investigated. Under optimal experimental conditions, the fluorescent nonwoven fabric exhibited a fluorescence intensity of 2.1 × 105 a.u. and a quantum yield of 6.35%. Additionally, the fluorescence intensity of the fluorescent nonwoven fabric decreased with the increase of aqueous copper concentration, and the quenching effect could be described by the Stern-Volmer equation. Furthermore, adjusting the pH of the aqueous copper at a fixed concentration revealed a linear relationship between the fluorescence intensity and pH. These observations demonstrate a dual response of the fluorescent nonwoven fabric to both aqueous copper and pH, enabling its potential application in the detection of both analytes.

Investigation of occurrence of aromatic amines in municipal wastewaters using passive sampling

Aromatic amines (AAs) are human-made compounds known for their mutagenic properties, entering surface waters from various sources, often originating as transformation products of dyes or pesticides. Despite their low concentrations in surface waters, AAs can exhibit mutagenicity. Our study focused on evaluating three passive samplers (PSs) for enriching these compounds from influent and effluent of a wastewater treatment plant (WWTP) in Brno, Czech Republic. The PSs tested included variants containing AttractSPE™ SDB-RPS sorbent disk, one with and one without a diffusive agarose hydrogel layer, and a modified Speedisk (Bakerbond Speedisk® H2O-Philic). PSs were deployed in wastewater (WW) for one to four weeks in various overlapping combinations, and the uptake of AAs to PSs was compared to their concentrations in 24-hour composite water samples. A targeted LC/MS analysis covered 42 amines, detecting 11 and 13 AAs in daily composite influent and effluent samples, respectively. In the influent, AAs ranged from 1.5 ng L−1 for 1-anilinonaphthalene to 1.0 μg L−1 for aniline, and the highest concentration among all measured amines was observed for cyclohexylamine at 2.9 μg L−1. In the effluent, concentrations ranged from 0.5 ng L−1 for 1-anilinonaphthalene to 88 ng L−1 for o-anisidine. PSs demonstrated comparable accumulation of amines, with integrative uptake up to 28 days in both influent and effluent and detection of up to 23 and 27 amines in influent and effluent, respectively; altogether 34 compounds were detected in the study. Sampling rates (Rs) were estimated for compounds present in at least 50 % of the samples and showing <40 % aqueous concentration variability, with robustness evaluated by comparing values for compounds in WWTP influent and effluent. Although all devices performed similarly, hydrogel-based PS exhibited superior performance in several criteria, including time integration and robustness of sampling rates, making it a suitable monitoring tool for AAs in WW.

Understanding the dynamics of enhanced light non-aqueous phase liquids (LNAPL) remediation at a polluted site: Insights from hydrogeophysical findings and chemical evidence

This study intricately unfolds a pioneering methodology for remediating contaminants in a persistent light non-aqueous phase liquids (LNAPL)-contaminated site. The remediation strategy seamlessly integrates enhanced desorption and in-situ chemical oxidation (ISCO), orchestrating the injection of PetroCleanze® (a desorbent) and RegenOx® (an oxidizer) through meticulously designed wells. These injections, based on detailed geological and hydrogeological assessments, aim at mobilizing residual contaminants for subsequent extraction. Real-time subsurface dynamics are investigated through geophysical monitoring, employing electrical resistivity tomography (ERT) to trace reagent migration pathways via their effect on bulk electrical conductivity. The integration of groundwater sampling data aims at providing additional insights into the transformations of contaminants in the spatiotemporal context. Vivid two-dimensional time-lapse ERT sections showcase the evolution of resistivity anomalies, providing high-resolution evidence of the heterogeneity, dispersion pathways of desorbent and oxidant, and residual LNAPL mobilization. Hydrochemical analyses complement this, revealing effective mobilization processes with increasing aqueous concentrations of total petroleum hydrocarbons (TPH) over time. Speciation analysis unveils the intricate interplay of desorption and oxidation, portraying the dynamic fractionation of hydrocarbon components. The hydrogeophysical and data-driven framework not only delivers qualitative and quantitative insights into reagent and contaminant distribution but also enhances understanding of spatial and temporal physio-chemical changes during the remediation process. Time-lapse ERT visually narrates the reagent's journey through time, while chemical analyses depict the unfolding processes of desorption and oxidation across space and time. The coupling of hydrogeophysical and chemical findings pictures the transformations of pollutants following the sequence of product injection and the push and pull activities, capturing the removal of mobilized contaminants through hydraulic barrier wells. This enhanced understanding proves instrumental towards optimizing and tailoring remediation efforts, especially in heterogeneous environmental settings. This study establishes a new standard for a sophisticated and innovative contaminant remediation approach, advancing environmental practices through the harmonized analysis of geophysical and chemical data.

Diagenetic iron-oxyhydroxides formed in suboxic to anoxic mine-impacted lake sediments near Sudbury, Ontario

Iron-oxyhydroxides are common in lake sediments, typically forming in oxidizing conditions near the sediment-water interface. However, in the mine-tailings-impacted sediment delta at Long Lake near Sudbury, Ontario, diagenetic Fe-oxyhydroxides are formed in suboxic-anoxic conditions. Geochemical and mineralogical techniques were applied to investigate the diagenetic transformations of tailings-derived oxidation products following burial in the sediment delta. Two sets of vertical cores were collected, one from a shallow-water location in the sediment delta near the lake shore and the other from a deeper-water location, approximately 90 m north from the mouth of the active channel. One core from each location was sectioned in the field into 0.1 m intervals using an anaerobic globe bag and porewater was extracted for aqueous geochemical analysis. The second core from each location was dried anaerobically and sub-sampled for solid-phase geochemical and mineralogical analyses. The aqueous concentrations of As, Fe, and SO4 are elevated near the sediment-water interface at both locations but at the shallow location they decline to the lowest observed concentrations at depth in the natural sediment. The decline in their concentrations may be enhanced by bacterial SO4 reduction and precipitation of Fe- and As-sulfides which were observed in mineralogical analysis. The mine-impacted sediment consists of numerous fragments of tailings-derived ferric-arsenate-cemented crusts. Compared to the cemented crusts that occur in the tailings, these fragments exhibit partial-dissolution features and SEM-EDS analyses demonstrate that they have relatively low As/Fe ratios, suggesting the occurrence of selective As(V) dissolution during diagenesis. Diagenetic Fe-oxyhydroxides occur throughout the mine-impacted sediment, including zones that contain diagenetic Fe- and As-sulfides, suggesting they may have formed in suboxic-anoxic conditions. They occur proximal to, but separate from, the fragments of tailings-derived crusts and display diverse morphologies, including what may be a previously unreported spherulitic form. Individual Fe-oxyhydroxides range in size from nm to μm but they mostly occur in delicate clusters suggesting they are autochthonous. Compared to the cemented crusts from the tailings, they contain very small amounts of As. Analysis of one spherule indicates it contains lepidocrocite microcrystals with amorphous SiO2.nH2O in the interstitial spaces. The microcrystals contain a mixture of Fe(III) and Fe(II), with Fe(III)/ΣFe = approximately 0.8. We interpret them to have formed by burst nucleation from Fe(III)-supersaturated solution, with subsequent aggregation of crystallites to form spherules.

Manganese exposure from spring and well waters in the Shenandoah Valley: interplay of aquifer lithology, soil composition, and redox conditions

Manganese (Mn) is of particular concern in groundwater, as low-level chronic exposure to aqueous Mn concentrations in drinking water can result in a variety of health and neurodevelopmental effects. Much of the global population relies on drinking water sourced from karst aquifers. Thus, we seek to assess the relative risk of Mn contamination in karst by investigating the Shenandoah Valley, VA region, as it is underlain by both karst and non-karst aquifers and much of the population relies on water wells and spring water. Water and soil samples were collected throughout the Shenandoah Valley, to supplement pre-existing well water and spring data from the National Water Information System and the Virginia Household Water Quality Program, totaling 1815 wells and 119 springs. Soils were analyzed using X-ray fluorescence and Mn K-Edge X-ray absorption near-edge structure spectroscopy. Factors such as soil type, soil geochemistry, and aquifer lithology were linked with each location to determine if correlations exist with aqueous Mn concentrations. Analyzing the distribution of Mn in drinking water sources suggests that water wells and springs within karst aquifers are preferable with respect to chronic Mn exposure, with < 4.9% of wells and springs in dolostone and limestone aquifers exceeding 100 ppb Mn, while sandstone and shale aquifers have a heightened risk, with > 20% of wells exceeding 100 ppb Mn. The geochemistry of associated soils and spatial relationships to various hydrologic and geologic features indicates that water interactions with aquifer lithology and soils contribute to aqueous Mn concentrations. Relationships between aqueous Mn in spring waters and Mn in soils indicate that increasing aqueous Mn is correlated with decreasing soil Mn(IV). These results point to redox conditions exerting a dominant control on Mn in this region.

Simultaneous time-resolved inorganic haloamine measurements enable analysis of disinfectant degradation kinetics and by-product formation.

We demonstrate the application of proton transfer time-of-flight mass spectrometry (PTR-TOF-MS) in monitoring the kinetics of disinfectant decay in water with a sensitivity one to three orders of magnitude greater than other analytical methods. Chemical disinfection inactivates pathogens during water treatment and prevents regrowth as water is conveyed in distribution system pipes, but it also causes formation of toxic disinfection by-products. Analytical limits have hindered kinetic models, which aid in ensuring water quality and protecting public health by predicting disinfection by-products formation. PTR-TOF-MS, designed for measuring gas phase concentrations of organic compounds, was able to simultaneously monitor aqueous concentrations of five inorganic haloamines relevant to chloramine disinfection under drinking water relevant concentrations. This novel application to aqueous analytes opens a new range of applications for PTR-TOF-MS.

Averting H+-Mediated Charge Storage Chemistry Stabilizes the High Output Voltage of LiMn2O4-Based Aqueous Battery.

H+ co-intercalation chemistry of the cathode is perceived to have damaging consequences on the low-rate and long-term cycling of aqueous zinc batteries, which is a critical hindrance to their promise for stationary storage applications. Herein, the thermodynamically competitive H+ storage chemistry of an attractive high-voltage cathode LiMn2O4 is revealed by employing operando and ex-situ analytical techniques together with density functional theory-based calculations. The H+ electrochemistry leads to the previously unforeseen voltage decay with cycling, impacting the available energy density, particularly at lower currents. Based on an in-depth investigation of the effect of the Li+ to Zn2+ ratio in the electrolyte on the charge storage mechanism, a purely aqueous and low-salt concentration electrolyte with a tuned Li+/Zn2+ ratio is introduced to subdue the H+-mediated charge storage kinetically, resulting in a stable voltage output and improved cycling stability at both low and high cathode loadings. Synchrotron X-ray diffraction analysis reveals that repeated H+ intercalation triggers an irreversible phase transformation leading to voltage decay, which is averted by shutting down H+ storage. These findings unveiling the origin and impact of the deleterious H+-storage, coupled with the practical strategy for its inhibition, will inspire further work toward this under-explored realm of aqueous battery chemistry.

Image analysis technique for quantifying fluorescein concentration profiles in clays

The image analysis technique approach links the dye concentration and color intensity, enabling quantification of spatial and temporal dye dynamics in clay media. In this study, batch adsorption tests and two-dimensional diffusion experiments with three types of clays (kaolinite, montmorillonite, and bentonite) were conducted for quantifying the vertical distribution of fluorescein dye tracer to evaluate the feasibility of the image analysis technique. In clay domains, color intensities were measured using images obtained during diffusion experiments, and these intensities were converted to aqueous fluorescein concentrations. Concentration profiles simulated from a one-dimensional analytical solution agreed well with those measured by the LRV technique with a single-channel application for kaolinite (blue channel, EB = 0.94 and 0.96) and montmorillonite (green channel, EG = 0.99 and 0.91) in the early (31.1, 54.6 PVs) and later (75.7, 93.9 PVs) diffusion times, respectively. The single-channel application for the bentonite was appropriate for concentration ranges of 0 − 400 mg/L for the blue channel and 400 − 1800 mg/L for the green channel. For quantifying the bentonite concentration profile with a wide range of dye concentrations (0 − 1800 mg/L), multi-channel application (blue + green channels) was required. Measured LRV concentration profiles with the multi-channel application showed better agreement (EB+G = 0.94) with simulated concentration profiles from the analytical solution than those with the single-channel application (EB = 0.56). The results of this study offer guidance on the application of the LRV approach as a non-destructive optical dye measurement method to diffusion problems between high and low permeability zones.

Expression of IL-4 and IL-12 in the aqueous humor of patients with chronic primary angle-closure glaucoma.

Angle-closure glaucoma is a common type of glaucoma in Asian populations. However, the role of inflammatory cytokines in angle-closure glaucoma is yet to be elucidated. Therefore, this study aimed to examine the expression of interleukin-4 (IL-4) and IL-12 in the aqueous humor of patients with chronic primary angle-closure glaucoma (CPACG) and elucidate the correlations between IL-4 and IL-12 concentrations in the aqueous humor, the degree of visual field defects, and retinal nerve fiber layer (RNFL) thickness in patients with CPACG. Aqueous humor samples were obtained from 31 patients diagnosed with CPACG at the Shaoxing People's Hospital between April 2022 and March 2023 and from 30 individuals with cataract (control). Based on the degree of the mean defect (MD), patients were divided into three groups: group A (MD ≤ -6dB, n= 10), group B (-6dB< MD< -12dB, n= 9), and group C (MD ≥ - 12dB, n= 12). RNFL thickness was measured using an optical coherence tomograph, and the concentrations of IL-4 and IL-12 in the aqueous humor were measured using Luminex technology. Aqueous humor concentration of IL-4 was significantly higher (p = 0.036) in the CPACG group than in the cataract group. However, there was no significant difference (p > 0.05) in IL- 12 concentration between the two groups. Additionally, there were no significant differences (p > 0.05) in IL-4 and IL-12 levels among patients with varying degrees of visual field defects (groups A, B, and C). Spearman's correlation analysis showed that IL-4 and IL-12 concentrations were not correlated (p > 0.05) with RNFL thickness around the optic disc and the degree of visual field defects. Conclusively, IL-4 may play an important role in the pathogenesis of CPACG. Given that IL-4 and IL-12 concentrations in the aqueous humor were not significantly correlated with RNFL thickness and the degree of visual field defects, the increase in IL-4 and IL-12 expression may not induce apoptosis and loss of retinal ganglion cells or affect RNFL thickness as well as the degree of visual field defects.

Sea and brackish water desalination through a novel PVDF-PTFE composite hydrophobic membrane by vacuum membrane distillation

The present study aims to evaluate the performance of porous hydrophobic Polyvinylidene fluoride − Polytetrafluoroethylene (PVDF-PTFE) composite membranes for desalination by vacuum membrane distillation (VMD) technique. The effect of operating parameters such as feed NaCl concentration (10,000 to 40,000 mg/L), feed temperature (50 °C to 80 °C), and downstream pressure (80 to 120 mmHg) on water permeation rate was studied. The increase in feed temperature enhanced the water permeation rate due to a rise in driving force across the membrane. For a constant downstream pressure of 80 mmHg, feed temperature of 80 °C and feed flow rate of 80 L/h, the membrane exhibited a maximum water flux of 3 kg/m2h with 99.86% salt rejection when aqueous NaCl concentration of 10,000 mg/L was charged as feed. Membrane characterization was performed using various analytical tools to determine physico-chemical properties such as pore size, structural elucidation, thermal stability, crystallinity, and hydrophobicity of the membrane material. Further, a temperature and concentration polarization coefficient-based analysis was performed by solving the mass and heat transport model equations using MATLAB software. The proposed research study promotes the application of VMD for recovering potable water from highly saline sea/brackish water and alleviates brine disposal issues.

Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers.

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments.

Direct visualization of pyrene diffusion in polyethylene and polyoxymethylene passive samplers

While passive sampling of ultra-low aqueous concentrations of hydrophobic organic compounds in environmental aqueous media has emerged as a promising analytical technique, there is a lack of good understanding of the fundamental diffusive processes. In this research, we used a fluorophore, pyrene, as a model compound to track diffusion in polymers through absorption and environmental media exchange processes. We directly tracked the penetration of pyrene into polyethylene (PE) and polyoxymethylene (POM) rods during absorption from water by sectioning the rod after different stages of absorption and observing the fluorescence signal through a microscope. Diffusion profiles of pyrene in polymers were simulated by numerical integration of Fickian diffusion. The results indicated that the uptake process in PE is governed by Fick's law and the absorption and desorption kinetics are similar in this polymer. However, the observed uptake profiles of pyrene in POM were non-Fickian and the release kinetics out of POM was slower compared to uptake into the polymer. We show that slower desorption from POM makes corrections for nonequilibrium using performance reference compounds (PRCs) problematic for deployments in water or sediment where there is significant advection. However, for static sediment deployments, the overall kinetics of exchange is controlled by slow transport through sediment and the hysteretic behavior of POM may not preclude the use of PRCs to interpret equilibrium status.

Comparison of lithium levels between suicide and non-suicide fatalities: cross-sectional study

IntroductionEcological studies have suggested the protective effect of micro-dose lithium in drinking water against suicide, however, the association between body lithium level and suicide is unknown.ObjectivesWe aimed to compare body lithium levels between suicide and non-suicide fatalities.MethodsThis cross-sectional study included 12 suicides and 16 non-suicides who were examined or dissected at the Tokyo Medical Examiner’s Office from March 2018 to June 2021. The aqueous humor lithium concentration was measured twice using inductively coupled plasma mass spectrometry. Analysis of covariance (ANCOVA) was used to compare the lithium concentration between suicides and non-suicides. Mixed-effects model was conducted to account for all lithium concentration data.ResultsThe aqueous humor lithium concentration did not change after death (t(7)=-0.70, SE=0.03, 95% CI=[-0.09, 0.05], P=0.51, Cohen’s d=0.01). The aqueous humor lithium concentration was lower in suicides (mean 0.50 μg/L (variance s2 0.04)) than in non-suicides (mean 0.92 μg/L (s2 0.07)) (t(26)=4.47, SE=0.09, 95% CI=[0.22 to 0.61], P&lt;0.001, Cohen’s d=1.71). The ANCOVA showed that death by suicide was significantly associated with lower lithium concentration (F(1, 24)=8.57, P=0.007), and the effect size was large (ηp2=0.26). The random intercept model showed a significant effect of suicide on aqueous humor lithium concentration (b=-0.261, SE=0.102, 95% CI=[-0.471 to -0.051], t(24)=-2.568, P=0.017).ConclusionsThe results of this study demonstrate that even micro-dose lithium is associated with suicide death. Clinical studies are warranted to examine the effects of micro-dose lithium on suicide prevention.Disclosure of InterestNone Declared

Mathematical and computational models for simulating transient nuclear criticality excursions within plutonium nitrate systems

This paper presents a novel methodology for the analysis of transient nuclear criticality in aqueous solutions of plutonium nitrate. The transient methodology includes one-dimensional thermal hydraulics and a detailed description of radiolytic gas formation (including aqueous concentrations of radiolysis species and bubble population, nucleation radius and advection velocity). The positive temperature feedback effect in dilute plutonium solutions, due to a low lying resonance (at ≈ 0.3 eV) in the microscopic fission cross section, is investigated. The solutions’ nuclear properties, such as intrinsic neutron source and mean neutron generation time; thermophysical properties and heat transfer coefficients; linear energy transfer and dynamics of radiolytic gas nucleation; and subcritical power, are also investigated. The effect of step and ramp reactivity insertions on transient nuclear criticality behaviour is examined, alongside the effect of fuel solution ingress and egress from the system. For a solution containing 16.0 g L−1 plutonium with an acidity of 0.2 mol L−1, increasing the width of the prescribed step reactivity insertion from 2.25 to 2.50 s increased the magnitude of the initial power peak, and decreased the time to boil, by an order of magnitude. It was observed that the characteristics of the radiolytic gas were dependent on the magnitude of the initial power peak. For example, the transients with the highest initial power peak produced an initially large quantity of radiolytic gas, with defined oscillations in their quantity (and other properties) as the transient progressed. For transients with lower power peaks, the oscillations became less defined, with a reduced period and magnitude, due to the lower quantity of radiolytic gas produced due to the initial power peak. Many of the presented simulations of nuclear criticality transients were terminated when the solution started to boil, a phenomenon which is not included in the presented methodology. Boiling occurred when the initial reactivity input induced a power spike that raised the solution temperature enough for the positive reactivity feedback effect to sustain the transient even when the reactivity input was removed.

Molecular Weight-Independent "Polysoap" Nanostructure Characterized via In Situ Resonant Soft X-ray Scattering.

Studying polymer micelle structure and loading dynamics under environmental conditions is critical for nanocarrier applications but challenging due to a lack of in situ nanoprobes. Here, the structure and loading of amphiphilic polyelectrolyte copolymer micelles, formed by 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and n-dodecyl acrylamide (DDAM), were investigated using a multimodal approach centered around in situ resonant soft X-ray scattering (RSoXS). We observe aqueous micelles formed from polymers of wide-ranging molecular weights and aqueous concentrations. Despite no measurable critical micelle concentration (CMC), structural analyses point toward multimeric structures for most molecular weights, with the lowest molecular weight micelles containing mixed coronas and forming loose micelle clusters that enhance hydrocarbon uptake. The sizes of the micelle substructures are independent of both the concentration and molecular weight. Combining these results with a measured molecular weight-invariant surface charge and zeta potential strengthens the link between the nanoparticle size and ionic charge in solution that governs the polysoap micelle structure. Such control would be critical for nanocarrier applications, such as drug delivery and water remediation.