Quantification of the dissolved organic matter effect on the sorption of hydrophobic organic pollutant: application of an overall mechanistic sorption model

This study presents an overall sorption model to estimate the sorption equilibrium coefficients of hydrophobic organic pollutants for heterogeneous aquatic systems. This proposed model combines a series of sorption equilibrium relationships including the adsorption of dissolved organic matters on particulates, the binding between organic pollutants and dissolved organic matters, and the sorption of organic pollutants on particulates with or without the presence of dissolved organic matters. By using this model, variations among the sorption equilibrium coefficients with the concentrations of dissolved organic matters are obtained. Also discussed herein are case studies involving pollutants having a wide spectrum of K(ow)s, different types of dissolved organic matters, different pH values and ionic strengths. In most of the case studies, the sorption equilibrium coefficients initially increase with the-concentrations of dissolved organic matters and, then, decrease after reaching a maximum value. This study also addresses the relative errors of partition coefficients attributed to the negligence of the effect caused by the dissolved organic matter, the so-called third-phase effect.     

Ni adsorption and Ni-Al LDH precipitation in a sandy aquifer: an experimental and mechanistic modeling study

Mining activities and industries have created nickel (Ni) contaminations in many parts of the world. The objective of this study is to increase our understanding of Ni adsorption and Nickel-Aluminium Layered Double Hydroxide (Ni-Al LDH) precipitation to reduce Ni mobility in a sandy soil aquifer. At pH ≥7.2 both adsorption and Ni-Al LDH precipitation occurred. In batch experiments with the sandy soil up to 70% of oxalate-extractable Al was taken up in LDH formation during 56 days. In a long term column experiment 99% of influent Ni was retained at pH 7.5 due to Ni adsorption (≈34%) and Ni-Al LDH precipitation (≈66%) based on mechanistic reactive transport modeling. The subsequent leaching at pH 6.5 could be largely attributed to desorption. Our results show that even in sandy aquifers with relatively low Al content, Ni-Al LDH precipitation is a promising mechanism to immobilize Ni.     

Sorption of Cu, Pb and Cr on Na-montmorillonite: competition and effect of major elements

The competitive sorption among Cu, Pb and Cr in ternary system on Na-montmorillonite at pH 3.5, 4.5 and 5.5 and at different heavy metal concentrations, and the effect of varying concentrations of Al, Fe, Ca and Mg on the sorption of heavy metals were studied. Competitive sorption of Cu, Pb and Cr in ternary system on montmorillonite followed the sequence of Cr ? Cu > Pb. Moreover, the competition was weakened by the increase of pH while was intensified by the increase of heavy metal concentration. The sorption of heavy metal on montmorillonite was inhibited by the presence of Ca and Mg, while Al and Fe showed different patterns in affecting heavy metal sorption. Aluminum and Fe generally inhibited the sorption of heavy metal when the pH and/or concentration of major elements were relatively low. However, promoting effects on heavy metal sorption by Al and Fe were found at relatively high pH and/or great concentration of major elements. The inhibition of major elements on heavy metal sorption generally followed the order of Al > Fe > Ca ? Mg, while Fe was more efficient than Al in promoting the sorption of heavy metals. These findings are of fundamental significance for evaluating the mobility of heavy metals in polluted environments.     

A pesticide emission model (PEM) Part I: model development

The application of pesticides to cultivated soil and crops is a major source of pesticides that are found in the atmosphere and which are transported and deposited to land and water surfaces over distances that range from local to global scales. In this first part of a two-part paper, a pesticide emission model (PEM) is proposed for estimating the exchange with the atmosphere of pesticides applied to soils and crops. The basis of PEM is a one-dimensional numerical solution of the dynamic equations describing the advection and diffusion of heat, moisture and pesticide within the soil column and exchange with the atmosphere through heat transfer, evapotranspiration and volatilization. The soil model is coupled with an atmospheric surface layer and a simple canopy model that includes: the interception of sprayed pesticide by the crop foliage; the partitioning of pesticide within a wet or dry canopy; and, the volatilization of pesticide to the atmosphere or the wash-off to the soil by precipitation. The finite-element technique used for solving the model equations is mass conservative and multi-year periods of simulation are possible while maintaining a proper mass balance of pesticide in the soil. The model is solved using 1200 s time-steps and 49 variably spaced levels in the soil to a depth of 2 m, with the highest vertical resolution (0.002 m spacing) near the soil surface. Similarity theory is used to parameterize the fluxes of heat, moisture and pesticide through the atmospheric surface layer with hourly meteorology being provided by either climate station observations or a meteorological model. In the second part to this paper, the results of an evaluation of PEM are reported.     

Part I: lead peroxide candles and dustfall collectors

A diffusion flame burner was operated to determine the effect of several parameters on the quantity of NO_x and unburned hydrocarbons produced. The statistical analysis indicated the unburned hydrocarbon emissions to be dependent upon the rate of heat release in the system, the amount of excess combustion air, the fuel molecular structure, and the interaction between the fuel structure and the amount of excess air. Analysis of the NO_x emissions, after an adjustment to a common temperature to eliminate the temperature effect, showed them to be dependent upon the fuel molecular structure and the amount of excess air. The NO_x emissions reached a maximum at the conditions which yielded minimum unburned hydrocarbon emissions. Multiple regressions were made which yielded predicting equations for both the unburned hydrocarbon and the NO_x for the apparatus used.     

A vehicle emissions system using a car simulator and a geographical information system: Part 1--System description and testing

A methodology for estimating vehicular emissions comprising a car simulator, a basic traffic model, and a geographical information system is capable of estimating vehicle emissions with high time and space resolution. Because of the extent of the work conducted, this article comprises two sections: In Part 1 of this work, we describe the system and its components and use examples for testing it. In Part 2 we will study in more detail the emissions of the sample fleet using the system and will make comparisons with another emission model. The experimental data for the car simulator is obtained using on-board measuring equipment and laboratory Fourier transform IR (FTIR) measurements with a dynamometer following typical driving cycles. The car simulator uses this data to generate emission factors every second. These emission factors, together with information on car activity and velocity profiles of highways and residential and arterial roads in Mexico City in conjunction with a basic traffic model, provide emissions per second of a sample fleet. A geographical information system is used to localize these road emissions.     

Fluorescence behaviour of Zn and Ni complexes of humic acids from different sources

Conventional fluorescence spectroscopy in the excitation, emission and synchronous scan modes and three-dimensional fluorescence spectroscopy in the form of an excitation-emission matrix (EEM) of fluorescence intensity as a function of excitation and emission wavelengths have been applied to the study of three humic acids (HAs) extracted from soil (SHA), peat (PHA) and compost (CHA) and their interaction products with Zn(II) and Ni(II) ions. Fluorescence spectra of HAs appear to be related to the nature and origin of the sample. A strong reduction of intensity of all peaks is observed in the spectra of HAs-metal complexes as compared to those of untreated HAs. Ni(II) exhibits greater quenching ability than Zn(II). Fluorescence quenching measured for complexes of HAs at increasing Ni(II) concentrations was linearly correlated with metal ion concentration. The different capacity to interact with metal ions showed by various HAs is attributed to their different molecular complexity.     

Critical Review of Environmental Forensic Techniques: Part I

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a compound, chemical associations with discrete type processes, chemical profiling, degradation models and contaminant transport models. These techniques, however, are rarely challenged or discussed in the literature relative to the scrutiny encountered in environmental litigation. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to review five types of forensic techniques and discuss their merits so that a user can decide which technique, or combination of techniques, is most appropriate for developing the technical portion of a case.     

Critical Review of Environmental Forensic Techniques: Part I

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a compound, chemical associations with discrete type processes, chemical profiling, degradation models and contaminant transport models. These techniques, however, are rarely challenged or discussed in the literature relative to the scrutiny encountered in environmental litigation. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to review five types of forensic techniques and discuss their merits so that a user can decide which technique, or combination of techniques, is most appropriate for developing the technical portion of a case.     

A prognostic physico-chemical model of secondary and marine inorganic multicomponent aerosols I. Model description

In this paper, the physico-chemical basics of the sectional multicomponent aerosol model SEMA are described. SEMA includes condensation and evaporation of sulphuric acid, nitric acid, hydrogen chloride, ammonia, and water vapour. The model can be applied to predictions of the chemical composition and size distribution of aqueous tropospheric secondary and marine aerosols. In SEMA, multicomponent thermodynamics and particle-size-dependent condensation and evaporation are efficiently coupled by application of a new sectional approach.     

Determination of Baghouse Performance from Coal and Ash Properties: Part I

Baghouse performance at utility coal-fired power plants is determined by baghouse design, operating procedures, and the characteristics of the ash that is collected as a dustcake on the fabric filter. The Electric Power Research Institute has conducted laboratory research to identify the fundamental properties of dustcake ash that influence baghouse performance. A database was assembled including measured characteristics of dustcake ash and data describing operating parameters and performance of full-scale and pilot-scale baghouses. Semi-empirical models were developed that describe the effects of particle morphology, particle size, ash cohesivity and ash chemistry on filtering pressure drop and particulate emissions. Cohesivity was identified as the primary ash characteristic affecting baghouse performance. Predictions of performance can be based on physical or chemical characterizations of the ash to be filtered. Part II of this article will discuss the effects of ash and coal chemistry, and baghouse design and operation on performance.     

Biosolids-amended soils: Part I. Effect of biosolids application on soil quality and ecotoxicity.

Investigations of potential risk from biosolids generally indicate that land application does not threaten human or ecosystem health, but questions continue to arise concerning the environmental effects of this practice. This research project was initiated to evaluate ecotoxicity resulting from the amendment of soils with biosolids from municipal wastewater treatment plants. Toxicity was evaluated using standard tests, including earthworm mortality, growth, and reproduction; seedling germination and root elongation; microbial respiration; and nematode mortality and reproduction. Nineteen municipal wastewater treatment plants were identified to participate in an initial screening of toxicity, and five were chosen for a more detailed evaluation. In addition, two soils with historically high applications of high-metal biosolids were evaluated. Contaminants examined were zinc, copper, nickel, chromium, arsenic, cadmium, lead, and coplanar polychlorinated biphenyls (PCBs). Single applications had no effect on soil metal concentrations. Coplanar PCBs were not detectable in any of the soils or biosolids. All target organisms were sensitive to reference toxicants. Limited toxicity was observed in a small number of the amended soils, but no patterns emerged. Approximately one-half of the negative effects of biosolids on bioindicators could be attributed to routine properties, such as slight depression of pH and/or elevated salinity. None of the accumulated metal concentrations were excessive, and most would not be considered elevated. These observations suggest that current regulations for application of biosolids to soils are providing adequate ecosystem protection.     

Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.     

Effects of Sorbent Injection on Participate Properties: Part I. Low-Temperature Sorbent Injection

Abstract

This article is the first of a two-part series dealing with the effects of sorbent injection processes on particulate properties. Part I reviews the effects on particulate properties of low-temperature sorbent injection processes (those processes that treat flue gas at temperatures near 300 °F). Part II reviews the effects on particulate properties of high-temperature sorbent injection processes (those processes that involve sorbent injection into the combustion or economizer sections of a boiler). In this article, we review what is currently known about the effects of the low-temperature sorbent injection processes on electrical resistivity, particulate mass loading, particulate size distribution, particulate morphology and cohesivity.

Mixtures of ash and sorbent produced by low-temperature sorbent injection processes are typically less cohesive than most types of fly ash. At temperatures within 30 °F of the water dew point, the combination of low cohesivity and low electrical resistivity of the ash and sorbent mixtures can cause electrical reentrainment in electrostatic precipitators. Deliquescent additives such as calcium chloride cause the water to be retained on the particle surface, thereby increasing cohesivity.

Sorbent injection has been reported to increase the particulate mass loading by a factor of 1.8 to 10, depending upon the reagent ratio and the coal sulfur content. Conventional and in-duct spray drying processes tend to shift the particle size distribution toward larger particles, while dry injection processes tend to shift the particle size distribution toward smaller particles.     

Implications of geographic variability on Comparative Toxicity Potentials of Cu, Ni and Zn in freshwaters of Canadian ecoregions

Current methods of estimating potential environmental impacts of metals in hazard and Life Cycle Impact Assessment (LCIA) do not consider differences in chemistry and landscape properties between geographic sites. Here, we developed and applied a model for regional aquatic impact characterization of metals using an updated method for estimating environmental fate factor (FF), bioavailability factor (BF) and aquatic ecotoxicity factor (EF). We applied the model to analyze differences in Comparative Toxicity Potentials (CTPs) of Cu, Ni and Zn for 24 Canadian ecoregions. The combined impacts of regional variability in ambient chemistry (in particular DOC, pH and hardness) and landscape properties (water residence time) can change the CTPs of these metals for freshwater by up to three orders of magnitude and change the relative ranking of metal hazard between ecoregions. Variation among Canadian freshwater chemistries and landscape characteristics influence the FFs within two orders of magnitude, BFs within two orders of magnitude for Ni and Zn and four orders of magnitude for Cu, and EFs within one order of magnitude. Sensitivity of metal FFs to environmental parameters alone spans three orders of magnitude when a constant water chemistry was used for all ecoregions. These results indicate that application of regionalised metal CTPs can have a significant influence in the analysis of ecotoxicological impacts in the life cycle assessment of products and processes.     

Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. Part II: hydrolysis reactions

The effect of dissolved humic acid (HA) on two types of hydrolysis reactions was investigated: (I) dehydrochlorination of gamma-hexachlorocyclohexane (HCH) and 1,1,2,2-tetrachloroethane (TeCA) as a reaction involving hydroxide ions (OH(-)) and (II) hydrolysis of 1-octyl acetate (OA) which is catalyzed by H(+) at the applied pH value (pH 4.5). The rate of TeCA hydrolysis was not affected by addition of 2 g l(-1) of HA at pH 10 (k' = 0.33 h(-1)) but HCH hydrolysis was significantly inhibited (k' = 4.6 x 10(-3) h(-1) without HA and 2.8 x 10(-3)h(-1) at 2 g l(-1) HA). HCH is sorbed by 51% whereas TeCA sorption is insignificant at this HA concentration. Sorbed HCH molecules are effectively protected due to electrostatic repulsion of OH(-) by the net negative charge of the HA molecules. In contrast, OA hydrolysis at pH 4.5 (k' = 1.6 x 10(-5) h(-1)) was drastically accelerated after addition of 2 g l(-1) HA (k' = 1.1 x 10(-3) h(-1)). The ratio of the pseudo-first-order rate constants of the sorbed and the freely dissolved ester fraction is about 70. H(+) accumulation in the microenvironment of the negatively charged HA molecules was suggested to contribute to the higher reaction rate for the sorbed fraction in case of this H(+)-catalyzed reaction. Analogous effects from anionic surfactants are known as micellar catalysis.     

Sulfadimethoxine and sulfaguanidine: their sorption potential on natural soils

Sulfonamides (SAs) are one of the oldest groups of veterinary chemotherapeutic agents. As these compounds are not completely metabolized in animals, a high proportion of the native form is excreted in feces and urine. They are therefore released either directly to the environment in aquacultures and by grazing animals, or indirectly during the application of manure or slurry. Once released into the environment, SAs become distributed among various environmental compartments and may be transported to surface or ground waters. The physicochemical properties of SAs, dosage and nature of the matrix are the factors mainly responsible for their distribution in the natural environment. Although these rather polar compounds have been in use for over half a century, knowledge of their fate and behavior in soil ecosystems is still limited. Therefore, in this work we have determined the sorption potential of sulfadimethoxine and sulfaguanidine on various natural soils. The influence on sorption of external factors, such as ionic strength and pH, were also determined. The sorption coefficients (K_d) obtained for the sulfonamides investigated were quite low (from 0.20 to 381.17 mL g⁻¹ for sulfadimethoxine and from 0.39 to 35.09 mL g⁻¹ for sulfaguanidine), which indicated that these substances are highly mobile and have the potential to run off into surface waters and/or infiltrate ground water. Moreover, the sorption of these pharmaceuticals was found to be influenced by OC, soil solution pH and ionic strength, with higher K_d values for soils of higher OC and lower K_d values with increasing pH and ionic strength.     

Ozonation of Procaine Penicillin G formulation effluent Part I: Process optimization and kinetics

Ozonation characteristics of synthetic Procaine Penicillin G (PPG) formulation effluent were investigated in a semi-batch ozone reactor at different pH (3, 7 and 12), ozone feed rates (600-2600 mg h-1) and COD values (200-600 mg l-1). Ozonation of aqueous PPG effluent resulted in 37 (82)% COD removal after 60 (120) min ozonation when the reaction pH was kept constant at pH=7.900 mg l-1 (corresponding to 50% of the total introduced) ozone was absorbed during a reaction period of 1 h. The effects of increasing the applied ozone dose and the initial COD on the COD abatement rates of PPG effluent were also studied. Results have indicated that increasing the ozone dose and decreasing the COD content both have positive effects on COD removal rates. The significant contribution of the free radical (.OH) reaction pathway to PPG ozonation could be traced using tert-butyl alcohol as the .OH probe compound at varying concentrations. The bimolecular reaction rate constants for the direct reaction of PPG with ozone were found as 152 and 2404 M-1 h-1 at pH=3 and 7, respectively, using the gas phase ozone partial pressures determined from of the outlet gas stream analysis. It could be demonstrated that ozone decomposition to free radicals being triggered by increasing the pH from 3 to 7 is essential for the rate enhancement of PPG effluent ozonation.     

The degradation of dyestuffs: Part I Primary biodegradation under anaerobic conditions

The paper describes a method for measuring the primary biodegradability of water soluble dyestuffs under anaerobic conditions and gives the results obtained on 22 dyes of commercial significance.     

Agro-waste biosorbents: Effect of physico-chemical properties on atrazine and imidacloprid sorption

Low cost agro-waste biosorbents namely eucalyptus bark (EB), corn cob (CC), bamboo chips (BC), rice straw (RS) and rice husk (RH) were characterized and used to study atrazine and imidacloprid sorption. Adsorption studies suggested that biosorbents greatly varied in their pesticide sorption behaviour. The EB was the best biosorbent to sorb both atrazine and imidacloprid with K_F values of 169.9 and 85.71, respectively. The adsorption isotherm were nonlinear in nature with slope (1/n) values <1. The Freundlich constant Correlating atrazine/imidacloprid sorption parameter [K_F.(1/n)] with the physicochemical properties of the biosorbents suggested that atrazine adsorption correlated significantly to the aromaticity, polarity, surface area, fractal dimension, lacunarity and relative C-O band intensity parameters of biosorbents. Probably, both physisorption and electrostatic interactions were responsible for the pesticide sorption. The eucalyptus bark can be exploited as low cost adsorbent for the removal of these pesticides as well as a component of on-farm biopurification systems.