A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.     

Investing in climate change adaptation and mitigation: A methodological review of real-options studies

Uncertain future payoffs and irreversible costs characterize investment in climate change adaptation and mitigation. Under these conditions, it is relevant to analyze investment decisions in a real options framework, as this approach takes into account the economic value associated with investment time flexibility. In this paper, we provide an overview of the literature adopting a real option approach to analyze investment in climate change adaptation and mitigation, and examine how the uncertain impacts of climate change on the condition of the human environment, risk preferences, and strategic interactions among decisions-makers have been modeled. We found that the complex nature of uncertainties associated with climate change is typically only partially taken into account and that the analysis is usually limited to decisions taken by individual risk neutral profit maximizers. Our findings call for further research to fill the identified gaps.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01342-8) contains supplementary material, which is available to authorized users.     

A review on management of chrome-tanned leather shavings: a holistic paradigm to combat the environmental issues

Raw hide/skins come to the tanners as a by-product of meat industry which is converted into value-added leather as product for fashion market. Leather manufacturing is a chemical process of natural biological matrix. It employs a huge quantity of water and inorganic and organic chemicals for processing and thereby discharges solid and liquid wastes into the environment. One of the potential solid wastes generated from leather industry is chrome-tanned leather shavings (CTLSs), and its disposal is increasingly becoming a huge challenge on disposal to tanners due to presence of heavy metal chromium. Hence, finding a sustainable solution to the CTLS disposal problem is a prime challenge for global tanners and researchers. This paper aims to the deeper review of various disposal methods on CTLS such as protein, chromium, and energy recovery processes and its utilization methodologies. Sustainable technologies have been developed to overcome CTLS solid wastes emanating from leather processing operations. Further, this review paper brings a broader classification of developed methodologies for treatment of CTLSs.     

A Receptor Climatology of Trajectories Originating in New York State

Air parcel trajectories originating from three locations in New York State are calculated for a three year period using the ARL-ATAD long-range transport model. Model output consisting of a trajectory segment's end point longitude and latitude position are analyzed to describe the long-range transport climatology by computing the frequency of occurrence of segment end points terminating over 33 receptor areas comprising east-central North America and a portion of the Atlantic Ocean. Results of the frequency of occurrence data show how often air pollutants emitted at or near the origin may be expected to drift over a specific downwind region. For the New York City airshed, it was found that 26.2% of the trajectories remain over New York State for transport times of 3 h and the frequency decreases to 5.2% after 24 h of transport. Approximately 40% of all trajectories are found to be over the Atlantic Ocean after 3 h of transport. When allowances are made for losses of data over the Atlantic Ocean, up to 64% of all trajectories are over the Atlantic Ocean after 24 h of transport. This frequency of trajectories over the Atlantic Ocean was found to be in agreement with wet and dry deposition modeling results conducted for power plants in New York City.     

Receptor Model Applied to Patterns in Space (RMAPS)

Abstract

The physical and mathematical bases of a new receptor model based on spatially intensive data are presented. The model apportions the average concentration of a species as measured at many sites among several spatially distinct sources and can be applied to primary or secondary species. In the latter case, no assumptions concerning transformation or deposition rates are required. The methodology is a combination of the empirical orthogonal function approach that is well known in meteorology and the self-modeling multivariate modeling approach that has long been applied in chemometrics and multivariate receptor modeling of air quality data. A simple, geometrical example of the modeling approach is given.     

Use of Project MOHAVE Perfluorocarbon Tracer Data to Evaluate Source and Receptor Models

ABSTRACT

Project MOHAVE was a major monitoring, modeling, and data analysis study whose objectives included the estimation of the contributions of the Mohave Power Project (MPP) and other sources to visibility impairment in the southwestern United States, in particular at Grand Canyon National Park. A major element of Project MOHAVE was the release of perfluorocarbon tracers at MPP and other locations during 50-day summer and 30-day winter intensive study periods. Tracer data (from about 30 locations) were sequestered until several source and receptor models were used to predict tracer concentrations. None of the models was successful in predicting the tracer concentrations; squared correlation coefficients between predicted and measured tracer were all less than 0.2, and most were less than 0.1.     

Long term quantitative ecological assessment of insecticides treatments in four African rivers: A methodological approach

In West Africa different insecticides had been applied in selected river areas for the reduction of the blackfly populations vectors of Onchocerca volvulus, a parasite causing blindness. To evaluate the possible long term effects of the larvicides on the non target fauna an aquatic monitoring programme has been up from the initial phase of the project. Addressing the attention to the invertebrates data collected in four countries during a maximum period ranging from 1977 to 1996, this paper shows and discusses the data analysis strategy for the measure and interpretation of the biological variation. In particular the application of quantitative ecological analysis methods. Principal Component Analysis, rank abundance models and the community diversity indexes, is critically discussed and comments are given to the ecological interpretation of the results.     

Decolorization and degradation of dyes with mediated fenton reaction.

A mediated Fenton system has been evaluated for decolorization of several types of dyes. The result shows that the Fenton system with a dihydroxybenzoic acid (DHBA) chelator-mediator effectively reduced the color of a diluted solution of Carta Yellow RW liquid, Carta Yellow G liquid, and Cartasol Red 2GF liquid dye to a colorless level after 90 minutes of treatment with 100 microM iron II (Fe[II]), 100 microM DHBA, and 10 mM hydrogen peroxide (H2O2) at room temperature. Our results show that compared to a neat Fenton process, the mediated Fenton decolorization process increased the production, and therefore the effective longevity, of hydroxyl radical (OH) species to increase the decolorization efficiency. Our results suggest that application of this system would also result in an increase in dissolved oxygen (DO) in solution, which in turn would result in reduction of chemical oxygen demand (COD), biochemical oxygen demand (BOD), and total organic carbon (TOC).     

Evaluating the sensitivity of a subsurface multicomponent reactive transport model with respect to transport and reaction parameters.

The input variables for a numerical model of reactive solute transport in groundwater include both transport parameters, such as hydraulic conductivity and infiltration, and reaction parameters that describe the important chemical and biological processes in the system. These parameters are subject to uncertainty due to measurement error and due to the spatial variability of properties in the subsurface environment. This paper compares the relative effects of uncertainty in the transport and reaction parameters on the results of a solute transport model. This question is addressed by comparing the magnitudes of the local sensitivity coefficients for transport and reaction parameters. General sensitivity equations are presented for transport parameters, reaction parameters, and the initial (background) concentrations in the problem domain. Parameter sensitivity coefficients are then calculated for an example problem in which uranium(VI) hydrolysis species are transported through a two-dimensional domain with a spatially variable pattern of surface complexation sites. In this example, the reaction model includes equilibrium speciation reactions and mass transfer-limited non-electrostatic surface complexation reactions. The set of parameters to which the model is most sensitive includes the initial concentration of one of the surface sites, the formation constant (Kf) of one of the surface complexes and the hydraulic conductivity within the reactive zone. For this example problem, the sensitivity analysis demonstrates that transport and reaction parameters are equally important in terms of how their variability affects the model results.     

Particle fluxes above forests: observations, methodological considerations and method comparisons

This paper reports a study designed to test, evaluate and compare micro-meteorological methods for determining the particle number flux above forest canopies. Half-hour average particle number fluxes above a representative broad-leaved forest in Denmark derived using eddy covariance range from -7x10(7) m(-2) s(-1) (1st percentile) to 5x10(7) m(-2) s(-1) (99th percentile), and have a median value of -1.6x10(6) m(-2) s(-1). The statistical uncertainties associated with the particle number flux estimates are larger than those for momentum fluxes and imply that in this data set approximately half of the particle number fluxes are not statistically different to zero. Particle number fluxes from relaxed eddy accumulation (REA) and eddy covariance are highly correlated and of almost identical magnitude. Flux estimates from the co-spectral and dissipation methods are also correlated with those from eddy covariance but exhibit higher absolute magnitude of fluxes.     

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.     

Receptor modeling for elemental source contributions to fine aerosols in New York State

Fine atmospheric particulate material was collected at five sites in upstate New York and analyzed for its trace element composition by instrumental neutron activation analysis. Of the 3700 daily samples collected over a 2-yr period, 1459 were analyzed for 39 elements, providing a large and detailed data set. Factor analysis (FA) was used to identify potential pollution sources or source regions and to construct inorganic source profiles for each. Following FA, the method of absolute factor scores-multiple linear regression was used to estimate the absolute elemental contribution of each of the identified sources. Factor analysis identified nine sources impacting the sampling region. Seven of these were found to be present in varying degrees among of the sampling sites. The other two sources had more localized impacts and were observed at only one of the sites each. Regional sources (such as the midwestern United States and eastern Canada) and crustal/soil material accounted for the greatest amount of the trace elements measured in the collected material.     

Receptor Modeling for Elemental Source Contributions to Fine Aerosols in New York State

ABSTRACT

Fine atmospheric particulate material was collected at five sites in upstate New York and analyzed for its trace element composition by instrumental neutron activation analysis. Of the 3700 daily samples collected over a 2-yr period, 1459 were analyzed for 39 elements, providing a large and detailed data set. Factor analysis (FA) was used to identify potential pollution sources or source regions and to construct inorganic source profiles for each. Following FA, the method of absolute factor scores-multiple linear regression was used to estimate the absolute elemental contribution of each of the identified sources. Factor analysis identified nine sources impacting the sampling region. Seven of these were found to be present in varying degrees among of the sampling sites. The other two sources had more localized impacts and were observed at only one of the sites each. Regional sources (such as the midwestern United States and eastern Canada) and crustal/ soil material accounted for the greatest amount of the trace elements measured in the collected material.     

Application of laser ablation ICP-MS and traditional techniques to the study of black crusts on building stones: a new methodological approach

Introduction  

In this work, we propose an innovative application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a methodological approach for the chemical characterisation of black crusts on stone monuments, associated with traditional micro-morphological (optical and scanning electron microscopy) and infrared spectroscopic techniques (FTIR).     

Degradation of 2,4-dichlorophenol by combining photo-assisted Fenton reaction and biological treatment.

The photo-Fenton reaction effect on the biodegradability improvement of 100 mg/L solution of 2,4-dichlorophenol (DCP) has been investigated. Biochemical oxygen demand (BOD) at 5 and 21 days, BODn/ chemical oxygen demand (COD) and BODn/total organic carbon (TOC) ratios, average oxidation state, and inhibition on activated sludge were monitored. For 50 mg/L hydrogen peroxide and 10 mg/L iron(II) initial concentrations and 40 minutes of reaction time in the photo-Fenton process, the biodegradability of the pretreated solution, measured as BOD5/COD ratio, was improved from 0 for the original DCP solution up to 0.18 (BOD21/COD = 0.24). At that point, all DCP was eliminated from the solution. To study the effect of the pretreatment step, the biological oxidation of pretreated solutions was tested in two semicontinuous stirred tank reactors, one operated with activated sludge and one with biomass acclimated to phenol. Results showed that more than 80% TOC removal could be obtained by codigestion of the pretreated solution with municipal wastewater. Total organic carbon removals of approximately 60% were also obtained when the sole carbon source for the aerobic reactors was the pretreated solution. The hydraulic retention times used in the bioreactors were of the same order of magnitude as those used at domestic wastewater treatment plants (i.e., between 12 and 24 hours). Kinetic studies based on pseudo-first-order kinetics have also been carried out. Constants were found to be in range 0.67 to 1.7 L x g total volatiles suspended solids(-1) x h(-1).     

A new methodological approach: The combined use of two-stage streaker samplers and optical particle counters for the characterization of airborne particulate matter

We describe a new experimental methodology based on the contemporary use of two-stage continuous streaker samplers and optical particle counters. This is a complementary approach to size-segregated particulate matter (PM) sampling, and it is able to give information on the elemental size distribution and to assess the contribution of major PM source to size bins. PM samples in the fine and coarse fraction of PM10 have been collected by a two-stage streaker sampler and analyzed by particle-induced X-ray emission (PIXE) to obtain elemental concentration time series with hourly resolution. PM sources and profiles were singled out by positive matrix factorization (PMF). A multi-linear regression of size-segregated number of particles versus the sources, resolved by PMF, made possible the apportionment of size-segregated particles number in a fast and direct way. Results obtained in three sampling sites, located in different urban districts are discussed.     

Local-scale fluxes of carbon dioxide in urban environments: methodological challenges and results from Chicago

Much attention is being directed to the measurement and modeling of surface-atmosphere exchanges of CO2 for different surface types. However, as yet, few measurements have been conducted in cities, even though these environments are widely acknowledged to be major sources of anthropogenic CO2. This paper highlights some of the challenges facing micrometeorologists attempting to use eddy covariance techniques to directly monitor CO2 fluxes in urban environments, focusing on the inherent variability within and between urban areas, and the importance of scale and the appropriate height of measurements. Results from a very short-term study of CO2 fluxes, undertaken in Chicago, Illinois in the summer of 1995, are presented. Mid-afternoon minimum CO2 concentrations and negative fluxes are attributed to the strength of biospheric photosynthesis and strong mixing of local anthropogenic sources in a deep mixed layer. Poor night-time atmospheric mixing, lower mixed layer depths, biospheric respiration, and continued missions from mobile and fixed anthropogenic sources, account for the night-time maxima in CO2 concentrations. The need for more, longer-term, continuous eddy covariance measurements is stressed.     

Influence of uncertain reaction rates on ozone sensitivity to emissions

Air quality models rely upon simplified photochemical mechanisms to efficiently represent the thousands of chemical species that interact to form air pollution. Uncertainties in the chemical reaction rate constants and photolysis frequencies that comprise those mechanisms can generate uncertainty in the estimation of pollutant concentrations and their responsiveness to emission controls. A high-order sensitivity analysis technique is applied to quantify the extent to which reaction rate uncertainties influence estimates of ozone concentrations and their sensitivities to precursor emissions during an air pollution episode in Houston, Texas. Several reactions were found to have much larger proportional effects on ozone’s sensitivities to emissions than on its concentrations. In particular, uncertainties in photolysis frequencies and in the rate of reaction between NO₂ and OH to form nitric acid can significantly influence the magnitude and sign of peak ozone sensitivity to nitrogen oxide (NO_x) emissions. Ozone sensitivity to VOCs exhibits a much more muted response to uncertainties in the reaction rate constants and photolysis frequencies considered here. The results indicate the importance of accurate reaction rate constants to predicting the ozone impacts resulting from NO_x emission controls.     

Application of a Chemical Mass Balance Receptor Model to Respirable Particulate Matter in Mexico City

Mexico City frequently experiences high levels of air pollution. This is due mainly to its topography and meteorology that suppress pollutant diffusion and dispersion. The atmospheric mixing is extremely poor, especially during the dry winter months. The levels of certain pollutants, such as particulate matter, are of concern since they have severe effects on public health. Visibility deterioration

is one of the most noticeable effects in large cities. Biological effects of particulate matter on man and animals, ranging from mild eye irritation to death, have been reported. The effects depend on the size of the particles, their solubility, and toxicity. The main objective of this paper is to present the results of a chemical mass balance receptor model applied to a well-characterized data set of particulate matter collected in the Mexico City Metropolitan Area (MCMA). Samples of particulate matter were collected using a denuder and a Hi-Vol system for the respirable fraction and total suspended particles, respectively.

In this paper the analysis of a database consisting of the chemical composition of 33 samples of respirable particulate matter (aerosols with diameter less than 2.5 μm) is presented. The 12-hour samples were acquired during day and night periods in a typical medium-income neighborhood from December 19, 1989 through February 5, 1990.

The results show that the main contributors to suspended particles are vehicles without catalytic converters and heavy-duty diesel vehicles. The contribution of refineries, smelters, cement plants, resuspended dust, natural sources, and secondary aerosols were taken into account. In particular, the vehicles without catalytic converters represent the major contribution to PM2.5. They contribute with 50% during the day and 38% at night. Most of the source profiles were taken from the model library SPECIATE EPA. However, native profiles for soil, vehicles, and refinery were designed.