Simple Mass Balance Equation Research Articles

Coupling of chromatography and precipitation for adjusting acidic variant content in a monoclonal antibody pool

The acidic charge variants (av) of monoclonal antibodies (mAb) are often reported to have reduced therapeutic potency compared with the main (mv) and basic variants (bv), therefore reduction in the av content in mAb pools is often prioritized over reduction in the bv content.In previous studies we described two different methods for reducing the av content, which were based on either ion exchange chromatography or selective precipitation in polyethylene glycol (PEG) solutions. In this study, we have developed a coupled process, in which advantages of simplicity and ease in realization of PEG-aided precipitation and high separation selectivity of anion exchange chromatography (AEX) were exploited. The design of AEX was supported by the kinetic-dispersive model, which was supplemented with the colloidal particle adsorption isotherm, whereas the precipitation process and its coupling with AEX was quantified by simple mass balance equations and underlying thermodynamic dependencies. The model was used to assess the performance of the coupling of AEX and precipitation under different operating conditions. The advantage of the coupled process over the stand-alone AEX depended on the demand for the av reduction as well as the initial variant composition of the mAb pool, e.g., the improvement in the throughput provided by the optimized sequence of AEX and PREC varied from 70 to 600% for the initial av content changed from 35 to 50% w/w, and the reduction demand changed from 30 to 60%.

Negative carbon isotope excursions: an interpretive framework

Numerous negative carbon isotope excursions (nCIEs) in the geologic record occurring over 104–105 years are interpreted as episodes of massive carbon release. nCIEs help to illuminate the connection between past carbon cycling and climate variability. Theoretically, the size of a nCIE can be used to determine the mass of carbon released, provided that the carbon source is known or other environmental changes such as temperature or ocean pH can be constrained. A simple isotopic mass balance equation often serves as a first order estimate for the mass of carbon input, but this approach ignores the effects of negative carbon cycle-climate feedbacks. Here we show, using 432 earth system model simulations, that the mass of carbon release and associated environmental impacts for a nCIE of a given size and carbon source depend on the onset duration of that nCIE: the longer the nCIE onset duration, the greater the required carbon input in order to counterbalance the input of 13C-enriched carbon through carbonate compensation and weathering feedbacks. On timescales >103 years, these feedbacks remove carbon from the atmosphere so that the relative rise in atmospheric CO2 decreases with the nCIE onset duration. Consequently, the impacts on global temperature, surface ocean pH and saturation state are reduced if the nCIE has a long onset duration. The framework provided here demonstrates how constraints on the total nCIE duration and relative shape—together determining the onset duration—affect the interpretation of sedimentary nCIEs. Finally, we evaluate selected well-studied nCIEs, including the Eocene Thermal Maximum 2 (∼54 Ma), the Paleocene–Eocene Thermal Maximum (∼56 Ma), and the Aptian Oceanic Anoxic Event (∼120 Ma), in the context of our model-based framework and show how modeled environmental changes can be used to narrow down the most likely carbon emissions scenarios.

Novel in vitro method for measuring the mass fraction of bioaccessible atmospheric polycyclic aromatic hydrocarbons using simulated human lung fluids

The bioaccessibility of organic pollutants is a key factor in human health risk assessments. We developed a novel in vitro method for determining the mass fraction of bioaccessible atmospheric polycyclic aromatic hydrocarbons (PAHs) using an air-washing device containing simulated human lung fluid. The experimental parameters were optimized based on the deposition fractions (DFs) of PAHs in human lung fluids. The DFs were measured for PAHs based on the mass of compounds in the mainstream and exhaled cigarette smoke. The mass fractions of bioaccessible PAHs were measured by passing the mainstream cigarette smoke through the air-washing device, and they were calculated via a simple mass balance equation based on the PAHs in the fluid and mainstream cigarette smoke. The DFs of individual PAHs ranged from 20.5% to 78.1%, and the bioaccessible mass fractions varied between 45.5% and 99.8%. The octanol-water partition coefficients (KOW) significantly influenced both the DFs and bioaccessible mass fractions of PAHs, and the optimized in vitro method could be used to estimate the bioavailable atmospheric PAHs. This in vitro method can potentially be used to measure the mass fraction of bioaccessible atmospheric PAHs and to assess the health risk related to human exposure to airborne PAHs.

Residual Capability of Alkali Binding by Hydrated Pozzolanic Cements in Long‐Service Concrete Structures

An experimental procedure was developed and applied to cement pastes made with two different pozzolanic cements (CEM IV/B (P) and CEM IV/B (V)) in order to ascertain the existence of a residual capability of alkali binding by long‐term hydrated pozzolanic cements and, at the same time, to evaluate the alkali retention capability and the concentration of OH− ions in the pore solution of such cementitious matrices. The developed procedure consisted of accelerated curing of cement paste specimens (150 days at 60°C and 100% RH), subsequent leaching tests at 60°C for 30 days by using deionized water or basic solutions (NaOH or KOH at different concentrations) as leaching media, and correlation of the leaching test results with a simple mass balance equation for sodium and potassium ions. The developed procedure was found to be appropriate for evaluating both the pore liquid alkalinity and the alkali retention capability by long‐term hydrated pozzolanic cement pastes. A residual capability of alkali binding was also identified for both tested pozzolanic cements, thus indicating their potential ability to prevent (CEM IV/B (V)) or minimize (CEM IV/B (P)) the risk of deleterious expansion associated with alkali‐aggregate reaction in long‐service concrete structures, like concrete dams.

Compositional Reservoir-Flow Simulation for Organic-Rich Gas Shale

Summary A new-generation compositional reservoir-flow-simulation model is presented for gas-bearing organic-rich source rocks, including convective/diffusive mass-balance equations for each hydrocarbon component in the organic (kerogen), inorganic, and fracture continua. The model accounts for the presence of dispersed kerogen with sorbed-gas corrected dynamic porosity. The Maxwell-Stefan theory is used to predict pressure- and composition-dependence of molecular diffusion in the formation. The equations are discretized and solved numerically by use of the control-volume finite-element method (CVFEM). The simulation is derived from a new multiscale conceptual flow model. We consider that kerogen is dispersed at a fine scale in the inorganic matrix and that it will be the discontinuous component of total porosity at the reservoir-simulation scale, which could be up to six orders of magnitude larger. A simple mass-balance equation is introduced to enable kerogen to transfer gas to the inorganic matrix that is collocated in the same gridblock. The convective/diffusive transport takes place between neighboring gridblocks only in the inorganic matrix. The simulation results show that the multiscale nature of the rock is important and should not be ignored because this could result in an overestimation of the contribution of the discontinuous kerogen. We also observe that although adsorbed fluid could contribute significantly to storage in the shale formation, its contribution to production could be severely limited by the lack of kerogen continuity at the reservoir scale and by a low degree of coupling between the organic and inorganic pores. The contribution of the Maxwell-Stefan diffusion to the overall transport in the shale formation increases as the inorganic matrix permeability is reduced because of pressure decline during production.

Theoretical and computational analyses of LNG evaporator

Theoretical and numerical analysis on the fluid flow and heat transfer inside a LNG evaporator is conducted in this work. Methane is used instead of LNG as the operating fluid. This is because; methane constitutes over 80% of natural gas. The analytical calculations are performed using simple mass and energy balance equations. The analytical calculations are made to assess the pressure and temperature variations in the steam tube. Multiphase numerical simulations are performed by solving the governing equations (basic flow equations of continuity, momentum and energy equations) in a portion of the evaporator domain consisting of a single steam pipe. The flow equations are solved along with equations of species transport. Multiphase modeling is incorporated using VOF method. Liquid methane is the primary phase. It vaporizes into the secondary phase gaseous methane. Steam is another secondary phase which flows through the heating coils. Turbulence is modeled by a two equation turbulence model. Both the theoretical and numerical predictions are seen to match well with each other. Further parametric studies are planned based on the current research.

The observation and evaluation of extensional filament deformation and breakup profiles for Non Newtonian fluids using a high strain rate double piston apparatus

Summary This paper reports a new design of experimental double piston filament stretching apparatus that can stretch fluids to very high extensional strain rates. Using high speed photography, filament deformation and breakup profiles of a strategically selected range of fluids including low and higher viscosity Newtonian liquids together with a viscoelastic polymer solution, biological and yield stress fluids were tested for the first time at extensional strain rates in excess of 1000 s−1. The stretching rate was sufficiently high that observation of low viscosity Newtonian fluid stretching, end pinching and break was observed during the stretching period of the deformation, whereas for a higher Newtonian viscosity, filament thinning and breakup occurred after the cessation of piston movement. Different fluid rheologies resulted in very different thinning and breakup profiles and the kinetics, in particular of yield stress fluids showed a striking contrast to Newtonians or viscoelastic fluids. Surprisingly all the tested fluids had an initial sub millisecond “wine glass” profile of deformation which could be approximately captured using a simple parabolic mass balance equation. Subsequent deformation profiles were however very sensitive to the rheology of the test fluid and where the final breakup occurred before or after piston cessation. In certain cases the thinning and break up was successfully matched with a 1D numerical simulation demonstrating the way numerical modelling can be used with the fluids correct rheological characterization to gain physical insight into how rheologically complex fluids deform and breakup at very high extensional deformation rates.

Solubility and modeling acid–base properties of adrenaline in NaCl aqueous solutions at different ionic strengths and temperatures

Solubility and acid–base properties of adrenaline were studied in NaCl aqueous solutions at different ionic strengths (0<I/molL−1<3.0) and temperatures (T=298.15 and 310.15K), by means of different techniques: potentiometry, UV-spectrophotometry and spectrofluorimetry. The intrinsic solubility of the ligand was calculated from simple mass balance equations, by using the free hydrogen concentration and the protonation constants of the ligand determined in the same experimental conditions of the solubility measurements. The salting-In or Out parameters and the activity coefficient of the neutral species were calculated by means of the Setschenow equation.The dependence of the protonation constants on the ionic strength was modeled by means of the Debye–Hückel type equation and of the SIT (Specific ion Interaction Theory) approach. The specific interaction parameters of the ion pairs were also reported. For the protonation constants, the following thermodynamic values at infinite dilution were obtained: T=298.15K, logK1H0=10.674±0.018 and logK2H0=8.954±0.022; T=310.15K, logK1H0=10.355±0.018 and logK2H0=8.749±0.030.

Thermodynamic Properties of Dopamine in Aqueous Solution. Acid–Base Properties, Distribution, and Activity Coefficients in NaCl Aqueous Solutions at Different Ionic Strengths and Temperatures

The acid–base properties of dopamine were studied in different experimental conditions by potentiometry, UV-spectrophotometry, and spectrofluorimetry. The distribution measurements between 2-methyl-1-propanol/pure water (or NaCl aqueous solutions up to I = 1.02 mol kg–1) were carried out at T = 298.15 K and 310.15 K. The potentiometric measurements were used to calculate the total concentration of the ligand in each phase, and from simple mass balance equations, using the free hydrogen concentration and the protonation constants, it was possible to calculate the ligand neutral species concentration and the distribution coefficient. The salting parameter and the activity coefficient of the neutral species were calculated by means of the Setschenow equation. Independently of the experimental conditions, a good agreement between the protonation constants obtained from the different techniques was obtained. The dependence of the protonation constants on ionic strength was modeled by means of the Debye–Huckel ...

Reviewing source water protection strategies: A conceptual model for water quality assessment

Source water protection (SWP) is the most important step in the implementation of a multi-barrier approach that ensures cost-effective delivery of safe drinking water. However, implementing SWP strategies can be a challenging task owing to technical and administrative issues. Decision support tools for effective implementation of SWP strategies can be very helpful that may lead to saving time and resources. This paper critically reviews different SWP strategies available for surface waters and also discusses various formulations for water quality assessment at the source. Source water quality regulations in Canada and other jurisdictions around the world are also discussed. Stormwater management ponds, vegetated filter strips, pollution control by effective agricultural practice (e.g., cover crop and crop rotation) and fencing are found to be frequently mentioned in those regulations. These strategies are discussed in details in terms of their key features to achieve the highest possible removal efficiencies for selected water quality parameters. Finally, a conceptual model is proposed to evaluate water quality changes at the source based on selected source water protection strategies. The model uses SWP strategies as a means to reduce possible pollutants in the source water. It also utilizes simple mass balance equations (dilution) to estimate the concentrations in the receiving water bodies and does not consider physico-chemical and other reactions. A surrogate measure, water quality index (WQI), based on selected water quality parameters, is used for the assessment of source water quality.

External gamma-ray dose rate and radon concentration in indoor environments covered with Brazilian granites

Health hazard from natural radioactivity in Brazilian granites, covering the walls and floor in a typical dwelling room, was assessed by indirect methods to predict external gamma-ray dose rates and radon concentrations. The gamma-ray dose rate was estimated by a Monte Carlo simulation method and validated by in-situ measurements with a NaI spectrometer. Activity concentrations of 232Th, 226Ra, and 40K in an extensive selection of Brazilian commercial granite samples measured by using gamma-ray spectrometry were found to be 4.5–450 Bq kg −1, 4.9–160 Bq kg −1 and 190–2029 Bq kg −1, respectively. The maximum external gamma-ray dose rate from floor and walls covered with the Brazilian granites in the typical dwelling room (5.0 m × 4.0 m area, 2.8 m height) was found to be 120 nGy h −1, which is comparable with the average worldwide exposure to external terrestrial radiation of 80 nGy h −1 due to natural sources, proposed by United Nations Scientific Committee on the Effects of Atomic Radiation. Radon concentrations in the room were also estimated by a simple mass balance equation and exhalation rates calculated from the measured values of 226Ra concentrations and the material properties. The results showed that the radon concentration in the room ventilated adequately (0.5 h −1) will be lower than 100 Bq m −3, value recommended as a reference level by the World Health Organization.

Determination of the stable carbon isotopic compositions of 2‐methyltetrols in ambient aerosols from the Changbai Mountains

Isoprene is one of the most important non-methane hydrocarbons (NMHCs) in the troposphere: it is a significant precursor of O(3) and it affects the oxidative state of the atmosphere. The diastereoisomeric 2-methyltetrols, 2-methylthreitol and 2-methylerythritol, are marker compounds of the photooxidation products of atmospheric isoprene. In order to obtain valuable information on the delta(13)C value of isoprene in the atmosphere, the stable carbon isotopic compositions of the 2-methyltetrols in ambient aerosols were investigated. The 2-methyltetrols were extracted from filter samples and derivatized with methylboronic acid, and the delta(13)C values of the methylboronate derivatives were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The delta(13)C values of the 2-methyltetrols were then calculated through a simple mass balance equation between the 2-methyltetrols, methylboronic acid and the methylboronates. The delta(13)C values of the 2-methyltetrols in aerosol samples collected at the Changbai Mountain Nature Reserves in eastern China were found to be -24.66 +/- 0.90 per thousand and -24.53 +/- 1.08 per thousand for 2-methylerythritol and 2-methylthreitol, respectively. Based on the measured isotopic composition of the 2-methyltetrols, the average delta(13)C value of atmospheric isoprene is inferred to be close to or slightly heavier than -24.66 per thousand at the collection site during the sampling period.

Modeling for plasma-enhanced catalytic reduction of nitrogen oxides

In this work, we simulated the whole processes of plasma-enhanced selective catalytic reduction for nitrogen oxides removal with hydrocarbon additive. The simulation model consists of plasma simulation and catalysis simulation. First, single filamentary microdischarge in dielectric barrier discharge was calculated to evaluate the radical production yield as a function of specific input energy. Second, the chemical reaction process in the discharge reactor was simulated to find the gas reforming property by the plasma. This plasma simulation was applied to NO oxidation process in atmospheric pressure N 2/O 2/NO/C 3H 6 mixtures under various discharge conditions. Finally, the catalytic reaction process was modeled using simple mass balance equations in gas-phase and on catalyst surface. The catalytic reaction simulation was tested for the reduction of nitrogen oxides on γ-Al 2 O 3 catalyst in N 2/O 2/NO/C 3H 6 and in N 2/O 2/NO 2/C 3H 6.

Gas chromatography/combustion/isotope ratio mass spectrometric analysis of the stable carbon composition of tetrols

The stable carbon isotope compositions of tetrols, erythritol and threitol were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using four tetrols with various delta(13)C values derivatized by methylboronic acid, the carbon isotope analysis method achieved excellent reproducibility and high accuracy. There was no carbon isotopic fractionation during the derivatization processes. The differences in the carbon isotopic compositions of methylboronates between the measured and calculated ranged from -0.20 to 0.12 per thousand, within the specification of the GC/C/IRMS system. It was demonstrated that delta(13)C values of tetrols could be calculated by a simple mass balance equation between tetrols, methylboronic acid, and methylboronates. The analogous 2-methyltetrols, marker compounds of photooxidation products of atmospheric isoprene, should have similar behavior using the same derivatization reagent. This method may provide insight on sources and sinks of atmospheric isoprene.

Model-Based Detection of Hydrogen Leaks in a Fuel Cell Stack

Hydrogen leaks are potentially dangerous faults in fuel cell systems that are fed with hydrogen-rich gas mixtures. This brief presents an approach to hydrogen leak detection and, thus, complements direct detection using hydrogen sensors. It relies on simple mass balance equations of an anode filling volume after taking into account the natural leak of the stack. A hydrogen mass flow, anode pressure, and relative humidity sensor are employed. Hydrogen leak detection without the use of relative humidity sensors is considered by employing adaptive alarm thresholds to eliminate false alarms. The validity of the method is also discussed in terms of common hydrogen supply system configurations. The detection method is validated using a 1.25-kW polymer electrolyte membrane fuel cell stack in a laboratory facility where leaks could be introduced in a controlled manner.

Estimates of critical acid loads and exceedances for forest soils across the conterminous United States

Concern regarding the impacts of continued nitrogen and sulfur deposition on ecosystem health has prompted the development of critical acid load assessments for forest soils. A critical acid load is a quantitative estimate of exposure to one or more pollutants at or above which harmful acidification-related effects on sensitive elements of the environment occur. A pollutant load in excess of a critical acid load is termed exceedance. This study combined a simple mass balance equation with national-scale databases to estimate critical acid load and exceedance for forest soils at a 1-km 2 spatial resolution across the conterminous US. This study estimated that about 15% of US forest soils are in exceedance of their critical acid load by more than 250 eq ha −1 yr −1, including much of New England and West Virginia. Very few areas of exceedance were predicted in the western US.

Uncertainty analysis on simple mass balance model to calculate critical loads for soil acidity

Simple mass balance equations (SMBE) of critical acid loads (CAL) in forest soil were developed to assess potential risks of air pollutants to ecosystems. However, to apply SMBE reliably at large scales, SMBE must be tested for adequacy and uncertainty. Our goal was to provide a detailed analysis of uncertainty in SMBE so that sound strategies for scaling up CAL estimates to the national scale could be developed. Specifically, we wanted to quantify CAL uncertainty under natural variability in 17 model parameters, and determine their relative contributions in predicting CAL. Results indicated that uncertainty in CAL came primarily from components of base cation weathering (BC w; 49%) and acid neutralizing capacity (46%), whereas the most critical parameters were BC w base rate (62%), soil depth (20%), and soil temperature (11%). Thus, improvements in estimates of these factors are crucial to reducing uncertainty and successfully scaling up SMBE for national assessments of CAL.

Dispersion of Heavy Metals (Metalloids) in Soils from 800-Year-Old Pollution (Mont-Lozère, France)

Numerous palaeo metallurgical sites (n = 70) characterized by slag presenting a homogeneous typology have been reported on the Mont-Lozère Massif (Southern France). These activities took place in the medieval period. The silicated slag matrix comprises mainly Pb (25%), Sb (0.4%), and several thousand parts per million of As, Cu, and Zn. Soil samples were collected in and around two sites, to understand the dispersion mechanism affecting the slag tailings through use of metal concentrations and lead isotopic compositions. The majority of polluted soil samples show high enrichment factors (EF) for Pb and Sb, slightly lower EFs for Cu, and much lower EFs for As and Zn. We show that this "old" metal pollution was physically dispersed, through erosion of workshop soils and slag tailings, in a restricted area (ca. 200 m down slope form the site). There is no evidence for massive leaching of slag metals by soil waters, except for Zn. Thus, the pollution is mainly due to the metal-making process, i.e., smoke-fallout, pieces of ore, the crackling of smelting ore outside the oven during reduction, and charcoal, etc. The lead isotopic compositions of the soils define a binary mixing trend between local granite or background soil and slag (which represent the workshop soil). Simple mass balance equations using either Pb isotopes or Pb concentrations suggest that between 40 and 100% of the total Pb in soils comes from the Medieval workshop pollution, leaving any later pollution negligible. The large number of sites on the Mont-Lozère means this medieval pollution is significant and poses a real environmental risk.

Seeding and Constant-Supersaturation Control by ATR-FTIR in Anti-Solvent Crystallization

The strategy for seeding and supersaturation control can play a critical role in defining the purity and particle size distribution of crystal products. Previous research has demonstrated that operation of crystallizers at constant supersaturation by feedback control is attractive due to its simplicity and resistance to operating disturbances. In this study, the effects of seed loading and seed size distribution were investigated for anti-solvent crystallization of paracetamol from a water−acetone mixture operated at constant supersaturation. A seeding strategy based on a simple mass balance equation provided a good starting point for the refinement of particle size distribution and adjustment of batch time in different circumstances to obtain a target average crystal size with narrow size distribution.

Development of a Compound-Specific Carbon Isotope Analysis Method for Atmospheric Formaldehyde via NaHSO3 and Cysteamine Derivatization

A novel method has been developed for the compound-specific carbon isotope analysis of atmospheric formaldehyde using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The method allows the determination of the delta13C value for atmospheric formaldehyde at nanogram levels with higher precision and lower detection limit. In the present work, atmospheric formaldehyde was collected using NaHSO3-coated Sep-Pak silica gel cartridges, washed out by water, then derivatized by cysteamine of known delta13C value, and the delta13C value of its derivative (thiazolidine) determined by GC/C/IRMS. Finally, the delta13C value of atmospheric formaldehyde could be calculated by a simple mass balance equation between formaldehyde, cysteamine, and thiazolidine. Using three formaldehydes with different delta13C values, calibration experiments were carried out over large ranges of formaldehyde concentrations. The carbon isotope analysis method achieved excellent reproducibility and high accuracy. There was no carbon isotopic fractionation throughout the derivatization processes. The differences in the carbon isotopic compositions of thiazolidine between the measured and predicted values were always <0.5 per thousand, within the specifications of the GC/C/IRMS system. The present method was also compared with the previous 2,4-dinitrophenylhydrazine derivatization method, and this method could be performed with lower analytical error and detection limit. Using this method, four 6-h ambient atmospheric formaldehyde samples were consecutively collected from 8 to 9 March 2005. The results showed that the delta13C values of atmospheric formaldehyde were different during the daytime and nighttime. This method proved suitable for the routine operation and may provide additional insight on sources and sinks of atmospheric formaldehyde.