Removal of Ni(II) from Aqueous Solutions by Nanoscale Magnetite

Magnetite nanoparticles were applied to remove Ni(II) from aqueous solutions as a function of pH, contact time, supporting electrolyte concentration, and analytical initial Ni(II) concentration. The highly crystalline nature of the magnetite structure with diameter of around 10 nm was characterized with transmission electron microscopy (TEM) and X‐ray diffractometry (XRD). The surface area was determined to be 115.3 m²/g. Surface chemical properties of magnetite at 25°C in aqueous suspensions were investigated. The point of zero charge (pHzpc) was found to be 7.33 and the intrinsic acidity constants (${\rm p}K_{{\rm a}1}^{{\rm s}} $ and ${\rm p}K_{{\rm a}2}^{{\rm s}} $ ) were found to be 9.3 and 5.9, respectively. The surface functional groups were investigated with Fourier transform‐infrared spectroscopy (FTIR) as well. Batch experiments were carried out to determine the adsorption kinetics and mechanism of Ni(II) by these magnetite nanoparticles. The adsorption process was found to be pH dependent. In NaCl solutions, Ni(II) adsorption increased with increasing ionic strength while in NaClO₄ solutions, Ni(II) adsorption exhibited little dependence on the ionic strength of the solution. The adsorption process better followed the pseudo‐second order equation and Freundlich isotherm.     

Photobleaching of chromophoric dissolved organic matter in natural waters: kinetics and modeling

The effects of monochromatic and polychromatic UV and visible (VIS) radiation on the optical properties (absorption and fluorescence) of chromophoric dissolved organic matter (CDOM) were examined for a Suwannee River fulvic acid (SRFA) standard and for water from the Delaware and Chesapeake Bays. The primary (direct) loss of absorption and fluorescence occurred at the irradiation wavelength(s), with smaller secondary (indirect) losses occurring outside the irradiation wavelength(s). The efficiency of both direct and indirect photobleaching decreased monotonically with increasing wavelength. Exposure to polychromatic light increased the CDOM absorption spectral slope (S), consistent with previous field measurements. An analysis of the monochromatic photobleaching kinetics argues that a model based on a simple superposition of multiple chromophores undergoing independent photobleaching cannot apply; this conclusion further implies that the absorption spectrum of CDOM cannot arise solely from a simple superposition of the spectra of numerous independent chromophores. The kinetics of CDOM absorption loss with the monochromatic irradiation were employed to create a simple, heuristic model of photobleaching. This model allowed us to examine the importance of the indirect photobleaching losses in determining the overall photobleaching rates as well as to model the photobleaching of natural waters under polychromatic light fields. Application of this model to natural waters closely predicted the change in the CDOM spectral shape caused by photodegradation. The time scale of this process was consistent with field observations acquired during the summertime for coastal waters in the Middle Atlantic Bight (MAB). The results indicate that the ratio of the photodegradation depth to the mixed layer depth is a key parameter controlling the rate of the photobleaching in surface waters.     

On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.     

Investigation of NaCl deliquescence in porous substrates using RH-XRD

We report on the use of X-ray diffractometry under controlled conditions of temperature and relative humidity (RH-XRD) for the investigation of NaCl deliquescence in the pore space of glass filter frits, which were used as model substrates. The study confirms that RH-XRD is an appropriate experimental technique for the in situ observation of phase transformation in porous materials. It is used for an investigation of both the deliquescence kinetics and the deliquescence humidity within pores of different median pore diameter. Several major influences affecting deliquescence rates in the pore space close to the surface of a porous material are discussed. It appears that quite short-term variation of ambient relative humidity, e.g., typical daily fluctuations, might induce damaging deliquescence–crystallization cycles within the pore space of building materials. In agreement with theoretical considerations it was found that confinement of NaCl crystals in pores with median diameters in the range 1.4–70 μm does not affect the deliquescence humidity of the salt.     

Practical kinetic modeling of petroleum generation and expulsion

Models for petroleum generation used by the industry are often limited by (a) sub-optimal laboratory pyrolysis methods for studying hydrocarbon generation, (b) over-simple models of petroleum generation, (c) inappropriate mathematical methods to derive kinetic parameters by fitting laboratory data, (d) primitive models of primary migration/expulsion and its coupling with petroleum generation, and (e) insufficient use of subsurface data to constrain the models. Problems (a), (b) and (c) lead to forced compensation effects between the activation energies and frequency factors of reaction kinetics that are wholly artificial, and which yield poor extrapolations to geological conditions. Simple switch or adsorption models of expulsion are insufficient to describe the residence time of species in source rocks. Yet, the residence time controls the thermal stresses to which the species are subjected for cracking to lighter species.     

封闭体系有机质与有机碳氢氮恢复动力学研究

在封闭体系的条件下,对典型的Ⅰ、Ⅱ、Ⅲ型干酪根在热演化过程中的损失进行生烃动力学研究,获得了Ⅰ、Ⅱ、Ⅲ型干酪根的总量、有机碳、氢以及氮质量损失动力学参数。用Kinetics软件计算了封闭体系干酪根有机碳丰度、氢碳原子比和氮碳原子比的恢复系数。认为在对高成熟—过成熟干酪根进行生烃评价时,Ⅰ、Ⅲ型干酪根残余有机碳丰度需要进行恢复,而Ⅱ型干酪根残余有机碳丰度不需要恢复。三种类型干酪根的氢碳原子比均需要进行恢复。     

Adsorption of Selenium Using Bagasse Fly Ash

The present work involves the study of Se(IV) adsorption onto bagasse fly ash. The adsorbents were coated with a ferric chloride solution for the effective removal of selenium. The physico‐chemical characterization of the adsorbent was carried out using standard methods, e. g., proximate analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, thermo‐gravimetric analysis and differential thermal analysis. Batch experiments were carried out to determine the effect of various parameters such as adsorbent dose, initial pH, contact time, and temperature on the adsorption process. Results obtained from these studies were analyzed using various kinetic models and isotherms. Se(IV) adsorption onto adsorbent was high at low pH values, and decreased with an increase in initial pH. A temperature study showed that the uptake of Se(IV) was greatest at 293 K, within the temperature range studied. The parameters of pseudo first order, pseudo second order, and Weber‐Morris intra‐particle kinetic models were determined. Equilibrium isotherms were analyzed using Langmuir, Freundlich, and Temkin isotherms. Error analyses were also carried out using hybrid fractional error function and Marquardt's percent standard deviation.     

Removal of Selenium by Adsorption onto Granular Activated Carbon (GAC) and Powdered Activated Carbon (PAC)

The present work involves the study of Se(IV) adsorption onto granular activated carbon (GAC) and powdered activated carbon (PAC). The adsorbents are coated with ferric chloride solution for the effective removal of selenium. The physico-chemical characterization of the adsorbents is carried out using standard methods, e. g., proximate analysis, scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), thermo-gravimetric (TGA) and differential thermal analysis (DTA), etc. The FTIR spectra of the GAC and PAC indicate the presence of various types of functional groups, e. g., free and hydrogen bonded OH groups, silanol groups (Si-OH), alkenes, and CO group stretching from aldehydes and ketones on the surface of adsorbents. Batch experiments are carried out to determine the effect of various factors such as adsorbent dose (w), initial pH, contact time (t), and temperature (T) on the adsorption process. The optimum GAC and PAC dosage is found to be 10 g/L and 8 g/L, respectively, for Se(IV) removal with C₀ = 100 mg/L. The percent removal of Se(IV) increases with increasing adsorbent concentration, while removal per unit weight of adsorbent increases with decreasing adsorbent concentration. Se(IV) adsorption onto both the GAC and PAC adsorbents is high at low pH values, and decreases with increased initial pH. The results obtained are analyzed by various kinetic models. The parameters of pseudo-first order, pseudo-second order kinetics, and Weber-Morris intra particle kinetics are determined. It is seen that the sorption kinetics of Se(IV) onto GAC and PAC can be best represented by the pseudo-second order kinetic model.     

Pesticides Removal Using Conventional and Low‐Cost Adsorbents: A Review

Worldwide pesticide usage has increased dramatically during the last three decades, coinciding with changing practices and increasing by intensive agriculture. This widespread use of pesticides for agricultural and non‐agricultural purposes has resulted in the presence of their residues in various environmental matrices. The occurrence of pesticides and their metabolite transported in rivers, channels, lakes, sea, air, soils, groundwater, and even drinking water, proves the high risk of these chemicals to human health and the environment. Therefore, pesticide removal is of an increasing concern. In this study, a review of the published literature dealing with pesticides removal process is presented. Firstly, pesticide removal by conventional means is briefly considered. Secondly, the use of the low‐cost sorbent through biosorption process is discussed comprehensively. The effect of factors such as pH, contact time, sorbent dosage, initial pesticide concentration, and optimization of biosorption conditions is also discussed. Kinetic, thermodynamic, and mechanism studies are also given. This study shows that both microorganisms and other materials with biological origin like agricultural by‐products may be used to this end. There is a significant potential for pesticide uptake by the use of various pristine and especially modified biosorbents. In the case of living organisms used as removal agents, degradation may also play a role in the total removal observed.