Fenton process for degradation of selected chlorinated aliphatic hydrocarbons exemplified by trichloroethylene, 1,1-dichloroethylene and chloroform

The degradation of selected chlorinated aliphatic hydrocarbons (CAHs) exemplified by trichloroethylene (TCE), 1,1-dichloroethylene (DCE), and chloroform (CF) was investigated with Fenton oxidation process. The results indicate that the degradation rate was primarily affected by the chemical structures of organic contaminants. Hydroxyl radicals (·OH) preferred to attack the organic contaminants with an electron-rich structure such as chlorinated alkenes (i.e., TCE and DCE). The dosing mode of Fenton’s reagent, particularly of Fe²⁺, significantly affected the degradation efficiency of studied organic compound. A new “time-squared” kinetic model, C = C _o exp(?k _obs t ²), was developed to express the degradation kinetics of selected CAHs. This model was applicable to TCE and DCE, but inapplicable to CF due to their varied reaction rate constants towards ?OH. Chloride release was monitored to examine the degree of dechlorination during the oxidation of selected CAHs. TCE was more easily dechlorinated thanDCE and CF.Dichloroacetic acid (DCAA) was identified as the major reaction intermediate in the oxidation of TCE, which could be completely removed as the reaction proceeded. No reaction intermediates or byproducts were identified in the oxidation of DCE and CF. Based on the identified intermediate, the reaction mechanism of TCE with Fenton’s reagent was proposed.     

Adsorption of cadmium from aqueous solution using Rooibos shoots as adsorbent

The use of Rooibos shoots, a natural adsorbent, for cadmium removal from wastewater is proposed. The effects of initial pH, adsorbent dosage, contact time, and initial concentration were investigated in the batch adsorption mode. The optimum pH was found to be 5.5. Isotherm and kinetic data were modeled; the data fitted best to the Freundlich model, and, kinetically, the adsorption was of pseudo-second order as shown by the high R² value of 0.9928 along with close agreement between the experimental q_e (13.9 mg g^?1) and calculated q_e (14.24 mg g^?1) values. The studied biomass material was found to be effectively used for removal of cadmium from contaminated mine wastewater.     

Wet oxidation of recalcitrant lignin water solutions: experimental and reaction kinetics

The purpose of the research was to study the behavior of lignin degradation under different conditions (T 110–190°C, pO₂ 0.5–1.5 MPa, pH 5, 9 and 12) and to develop a predictive model. Temperature increase improved lignin removal from 75% at 110°C to 100% at 190°C (experimental). Increasing the pH enhanced the lignin removal efficiency from 30 to 97% (experimental). The developed model predicted the lignin degradation and changes in COD, BOD and TOC. The model agreed well with the experimental data (R ² = 0.93 at pH 5 and 12).     

Adsorption of cationic and anionic surfactants onto organic polymer resin Lewatit VPOC 1064 MD PH

The adsorption of a cationic (CTAB, cetyl trimethylammonium bromide) and an anionic surfactant (SLES, sodium dodecylethersulfate) from aqueous solution onto organic polymer resin (Lewatit VPOC 1064 MD PH) was studied. A series of batch experiments were performed to determine the sorption isotherms of surfactants to organic polymer resin. The experimental studies were analyzed by Langmuir and Freundlich isotherms. Furthermore, the isotherm parameters, average percentage errors (ε) of model data, and separation factor (R _L) were calculated. Other factors influencing the adsorption capacity (contact time, adsorbent amount, and initial surfactant concentration) were also discussed. The experimental data fitted very well to the Langmuir equilibrium model in the studied concentration range. The calculated R _L values showed that the adsorption of both surfactants were favorable. Among the surfactants, CTAB showed higher adsorption capacity onto organic polymer resin compared to SLES (Q ⁰ = 250 and 34.36 mg g⁻¹, respectively).     

Assessment of methane from agricultural field during the entire paddy cropping seasons – a case study

A systematic effort was made to assess the emission of methane from paddy fields using closed chamber technique. Methane emission measurements were performed over a year during the Kharif (wet season), Rabi (dry season), and fallow periods. Various soil parameters like redox potential, organic carbon and ferrous ion were determined to evaluate their control on methane emissions. Diurnal measurement of the flux showed a minimum (0.44?mg?m^?2?h^?1) in the morning (8?a.m.), which increased gradually to a value of 1.16?mg?m^?2?h^?1 till the evening due to the rise in soil temperature. The seasonally integrated flux (E _SIF) for CH₄ was calculated. The E _SIF for methane during Kharif and Rabi crops were found to be 5.97?g?m^?2 and 2.59?g?m^?2, respectively. It was observed that the methane flux was maximum during flowering and fertilizer application stages for both paddy cropping seasons. The redox potential was low and the ferrous ion was higher during flowering and tiller stages. The methane emission was higher at E _AIF) was calculated for methane to make a budget estimate of methane emission from rice cultivated under rain fed drought prone water regime.     

Removal of contaminants in leachate from landfill by waste steel scrap and converter slag

This study may be the first investigation to be performed into the potential benefits of recycling industrial waste in controlling contaminants in leachate. Batch reactors were used to evaluate the efficacy of waste steel scrap and converter slag to treat mixed contaminants using mimic leachate solution. The waste steel scrap was prepared through pre-treatment by an acid-washed step, which retained both zero-valent iron site and iron oxide site. Extensive trichloroethene (TCE) removal (95%) occurred by acid-washed steel scrap within 48 h. In addition, dehalogenation (Cl⁻ production) was observed to be above 7.5% of the added TCE on a molar basis for 48 h. The waste steel scrap also removed tetrachloroethylene (PCE) through the dehalogenation process although to a lesser extent than TCE. Heavy metals (Cr, Mn, Cu, Zn, As, Cd, and Pb) were extensively removed by both acid-washed steel scrap and converter slag through the adsorption process. Among salt ions (NH₄⁺, NO₃⁻, and PO₄³⁻), PO₄³⁻ was removed by both waste steel scrap (100% within 8 h) and converter slag (100% within 20 min), whereas NO₃^- and NH₄⁺ were removed by waste steel scrap (100% within 7 days) and converter slag (up to 50% within 4 days) respectively. This work suggests that permeable reactive barriers (PRBs) with waste steel scrap and converter slag might be an effective approach to intercepting mixed contaminants in leachate from landfill.     

Survival and sex ratios of the intertidal copepod,Tigriopus californicus,following ultraviolet-B (290–320 nm) radiation exposure

The marine harpacticoid copepod, Tigriopus californicus (Baker), is a successful colonizer of supralittoral splash pools from Torch Bay, Alaska, to Baja California, Mexico. As these pools are subject to abundant amounts of direct solar radiation, it was of interest to determine the sensitivity of T. californicus to ultraviolet-B (UV-B, 290 to 320 nm) radiation. During 1980, copepods were raised under diurnal conditions in the laboratory and fed a mixture of unicellular algae and bacteria. Larval and adult stages were irradiated for 0 to 26 h on a rotating turntable under enhanced ultraviolet radiation. Following irradiation, the copepods were maintained in the culture area and checked daily for survival. All life stages of T. californicus tolerated enhanced UV-B radiation irrespective of exposure period; in contrast, survival of an irradiated planktonic copepod, Acartia clausii (Giesbrecht), was significantly lower. Additionally, there appeared to be asex ratio shift in adults that developed from the youngest naupliar stages (N₁/N₂) of T. californicus that were irradiated. Extraction and tentative identification of the pigment(s) responsible for the bright orange color of the carapace of T. californicus were performed. These pigments may function to absorb UV radiation and protect internal structures from photochemically induced damage.     

Steam activation,characterisation and adsorption studies of activated carbon from maize tassels

In this paper, steam-produced activated carbon (STAC) from maize tassel (MT) was evaluated for its ability to remove basic dye (methylene blue MB) from aqueous solution in a batch adsorption process. The equilibrium experiments were conducted in the range of 50–300 mg/L initial MB concentrations at 30°C, for effect of pH, adsorbent dosage and contact time. The experimental data were analysed by Langmuir, Freundlich and Temkin isotherm models of adsorption. Freundlich adsorption isotherm was found to have highest value of R²(R²=0.97) compared to other models of Langmuir and Temkin having (0.96 and 0.95 respectively). STAC has a high adsorptive capacity for MB dye (200 mg/g) and also showed favourable adsorption for the dye with the separation factor (R_L<1) for the dye-activated carbon system. The kinetic data obtained were analysed using pseudo first-order kinetic equation and pseudo second-order kinetic equation. The experimental data fitted well into pseudo second-order kinetic equation, as demonstrated by the high value of R².     

PIXGRO: A model for simulating the ecosystem CO2 exchange and growth of spring barley

A model, PIXGRO, developed by coupling a canopy flux sub-model (PROXEL_NEE; PROcess-based piXEL Net Ecosystem CO₂ Exchange) to a vegetation structure submodel (CGRO), for simulating both net ecosystem CO₂ exchange (NEE) and growth of spring barley is described. PIXGRO is an extension of the stand-level CO₂ and H₂O-flux model PROXEL_NEE, that simulates the NEE on a process basis, but goes further to include the dry matter production, partitioning, and crop development for spring barley. Dry matter partitioned to the leaf was converted to leaf area index (LAI) using relationships for the specific leaf area (SLA). The canopy flux component, PROXEL_NEE was calibrated using information from the literature on C3 plants and was tested using CO₂ flux data from an eddy-covariance (EC) method in Finland with long-term observations. The growth component (CGRO) was calibrated using data from the literature on spring barley as well as data from the Finland site. It was then validated against field data from two sites in Germany and partly via the use of MODIS remotely sensed LAI from the Finland site.Both the diurnal and the seasonal patterns of gross CO₂ uptake were very well simulated (R² = 0.92). A slight seasonal bias may be attributed to leaf ageing. Crop growth was also well simulated; simulated dry matter agreed with field observed data from Germany (R² = 0.90). For LAI, the agreement between the simulated and observed was good (R² = 0.80), giving an indication that functions describing the conversion of fixed CO₂ to dry matter and the subsequent partitioning leaf dry matter and LAI simulation were robust and provided reliable estimates.The MODIS LAI at a resolution of 1000 m agreed poorly (R² = 0.45) with the PIXGRO simulated LAI and the observed LAI at the Finland site in 2001. We attributed this to the coarse resolution of the image and/or the small size of the barley field (about 17 ha or 0.25 km²) at the Finland site. By deriving a regression relation between the observed LAI and NDVI from a higher resolution MODIS (500 m resolution), the MODIS-recalculated LAI agreed better with the PIXGRO-simulated LAI (R² = 0.86).PIXGRO provides a prototype model bridging the disciplines of plant physiology, crop modeling and remote sensing, for use in a spatial context in evaluating carbon balances and plant growth at stand level, landscape, regional, and with some care, continental scales. Since almost 50% of the European land surface is covered by crops, such a model is needed for the dynamic estimation of LAI and NEE of croplands.     

Removal of congo red and basic violet 1 by chir pine (Pinus roxburghii) sawdust,a saw mill waste: batch and column studies

The efficiency of chir pine sawdust (CPS) for adsorptive removal of the dyes, congo red (CR) and basic violet 1 (BV), from aqueous solution was evaluated using batch and column studies. The equilibrium was attained in 60 min for CR and 45 min for BV. The adsorption of BV obeyed the Langmuir isotherm model while the Freundlich isotherm fitted the equilibrium data of CR adsorption. The Langmuir monolayer adsorption capacities (Q_o) of CPS for BV and CR were 11.3 and 5.8 g kg^?1, respectively. The kinetic data for CR were best fitted to the Lagergren pseudo-first-order model and for BV to the pseudo-second-order model. The intra-particle diffusion was found to be the rate-controlling step for CR adsorption, while the adsorption kinetics of BV were controlled by both intra-particle and liquid-film diffusion. The thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic in nature. The adsorption activation energy (E_a) for CR (124 kJ mol^?1) implied chemical adsorption while that for BV (5.4 kJ mol^?1) indicated physical adsorption. An increase in the Thomas model constant (K_Th) with increasing flow indicated that for both dyes the mass transport resistance decreased during adsorption. Thus, CPS may be an efficient low-cost adsorbent for decolorization of dye-containing wastewaters.     

Adsorptive removal of rhodamine B from textile wastewater using water chestnut (Trapa natans L.) peel: adsorption dynamics and kinetic studies

Water chestnut peel, an agricultural bio-waste, was used as a biosorbent for removal of rhodamine B (RhB), basic textile dye, from an aqueous solution. The effects of various experimental parameters were studied. The equilibrium data correlated well with a Freundlich isotherm (R² = 0.98–0.99) followed by a Halsey isotherm model (R² = 0.98–0.99) which indicated heterogeneity of the adsorbent surface and multilayer adsorption of RhB dye onto the water chestnut peel waste (WCPW). High correlation coefficients (R² = 0.99) together with close agreement between experimental q_e (0.4–1.7 mg g^?1) and calculated q_e (0.4–2.5 mg g^?1) suggested that the adsorption process followed pseudo-second-order kinetics, with k₂ values in the range of 52–3.4 × 10^?1 g mg^?1 min^?1 at different concentrations. The overall mechanism of adsorption was controlled by both liquid-film and intra-particle diffusions. The negative values of change in Gibb's free energy (?ΔG⁰ = 19.2–29.2 kJ mol^?1) and positive values of change in enthalpy (ΔH⁰ = 30.9–117.6 kJ mol^?1) revealed the process to be spontaneous and endothermic. WCPW was found to be an effective adsorbent for removal of RhB, a cationic dye, from an aqueous solution.     

Experimental analysis of Froude number effect on air entrainment in the hydraulic jump

A hydraulic jump is characterized by strong energy dissipation and mixing, large-scale turbulence, air entrainment, waves, and spray. Despite recent pertinent studies, the interaction between air bubbles diffusion and momentum transfer is not completely understood. The objective of this paper is to present experimental results from new measurements performed in a rectangular horizontal flume with partially developed inflow conditions. The vertical distributions of the void fraction and the air bubbles count rate were recorded for inflow Froude number Fr ₁ in the range from 5.2 to 14.3. Rapid detrainment process was observed near the jump toe, whereas the structure of the air diffusion layer was clearly observed over longer distances. These new data were compared with previous data generally collected at lower Froude numbers. The comparison demonstrated that, at a fixed distance from the jump toe, the maximum void fraction C _max increases with the increasing Fr ₁. The vertical locations of the maximum void fraction and bubble count rate were consistent with previous studies. Finally, an empirical correlation between the upper boundary of the air diffusion layer and the distance from the impingement point was derived.     

A simulation model for the management of vicuña populations

The population dynamics of the vicuña was modelled based on field data from the Central Galeras Sector, Perú. Rains were simulated in order to obtain net primary productivity and grass availability which act upon density-dependent fecundity and mortality. The model produces a population growth curve that tends to stabilize at densities around 100 vicuñas per km². Harvest and shearing processes were simulated as part of the vicuña population management model. Harvest was based upon a fixed threshold density D_e below which no harvest occurs; for densities above D_e harvesting is applied at a rate proportional to the difference between D_e and the current population density (fixed escapement or ‘bang-bang’ harvest rule). Management optimization was analyzed by determining the optimal escapement density D_e, which maximized either net profits or the number of animals harvested. Analyzing the results as cumulative totals over 20 years of simulation, an optimum harvest production was obtained for a D_e of about 40 vicuñas per km², and maximum profit was obtained for a D_e around 70 vicuñas per km². Analyzing the results of 20 years of simulation as annual averages with an original population density of 40 vicuñas per km², the harvest production and profits were maximized for a D_e of 40 and 60 vicuñas per km², respectively.The model was validated using data from the Reserva Nacional San Guillermo, Argentina, where vicuña and guanaco populations coexist (although their interaction was not modelled). The sensitivity analysis was performed with three different techniques: (a) stepwise multiple linear regression, (b) visual graphic analysis based on a polar coordinates system, and (c) direct evaluation of the effect on management decisions. The curve shape parameters of the fecundity and mortality functions proved to be the most important ones in determining the outcome of the model.     

菲和镉单一及复合污染条件下在毛蚶体内的富集动力学研究

采用室内半静态双箱动力学模型实验,研究了菲和镉单一及复合污染条件下在毛蚶(Anadara subcrenata)体内的生物富集,通过对富集与释放过程中毛蚶体内菲和Cd的富集量进行非线性曲线拟合,获得了菲和Cd单一及复合污染条件下在毛蚶体内的吸收速率常数k1、释放速率常数k2、生物富集因子BCF、生物半衰期B1/2和平衡状态下最大富集量CA max等动力学参数。实验结果表明,菲和Cd在实验前期富集速率较高,8 d以后富集速率减缓,释放阶段与富集阶段相似。毛蚶对菲的BCF值为37.80,远大于Cd的BCF值13.12,且生物半衰期时间更长,菲更容易在生物体内富集。菲和Cd联合暴露条件下,在毛蚶体内的CA max和BCF值均大于单一作用,说明二者同时暴露时,毛蚶对菲和镉的吸收富集均有所增强。实验模型拟合度较好,输出值和实测值之间无显著性差异,拟合方程和拟合参数可信。     

Biogeochemistry of aromatic hydrocarbons in the benthos of microcosms†

Investigations into the fate of petroleum compounds in the marine environment were carried out using experimental microcosms of two sizes and designs. Aromatic hydrocarbons or No. 2 fuel oil were spiked to the water of a 13 m³ continuous flow system and to a 2281 recycled flow system. The transport and alteration of this oil was traced in the sediment and benthic organisms (Glycera americana, Crepidula sp., and Nephtys incisa) of these microcosms. Measurable contamination was found in both sample types. The aromatic hydrocarbon distribution, including relative isomeric distribution (e.g., C₂‐phenanthrenes) was found to be different in sediment and in organisms from that which was originally introduced to the experimental microcosm. Differences in isomer distribution between Glycera and Crepidula were also detected. Based on the experimental data: molecular weight and specific isomeric form, biochemical processes, solubility, and particle adsorption/desorption influence the fate of petroleum compounds in benthic ecosystems.     

Effect of initial ratio of heavy metal to biomass on growth yield in batch culture of activated sludge

The effect of heavy metal on the observed growth yield (y_obs) was observed in batch culture of activated sludge. However, no attention has been paid to quantitatively describe the relationship between heavy metal concentration and y_obs so far. In this study, a growth yield model in relation to the ratio of initial heavy metal concentration (C_m) to initial biomass concentration (X ₀) was proposed for batch culture of activated sludge, and was verified with experimental and literature data. A significant decline in Y_obs was found with the increase of the C_m/X₀ ratio. It was clearly demonstrated that for a given initial heavy metal concentration, real strength of heavy metal exerted on unit biomass would be reduced with the increase of initial biomass concentration. This study for the first time revealed that the toxicity of heavy metal to microbial growth should be correlated with the C_m/X₀ ratio rather than to C_m only. A concept of effective C_m/X₀ ratio, namely (C_m/X₀ )₅₀ was then developed for more reasonably and reliably assessing toxicity of heavy metal to microorganisms.     

Biosorption of cadmium and nickel ions using marine macrophyte,Cymodocea nodosa

ABSTRACT

Seagrass (Cymodocea nodosa) ability to remove cadmium and nickel ions from single metal solutions was investigated in the present study. Metal ions were measured in the solution using an atomic absorption spectrophotometer. Various operational parameters (initial pH, biomass dose, metal ion concentration, and contact time) were tested and found to affect the uptake capacity of Cd (II) and Ni (II). More than 70% of biosorption capacity occurred in the first few minutes for both metal ions. The pseudo-second-order kinetic model and the Langmuir model were found to best fit the experimental data of Cd (II) and Ni (II) biosorption. The maximum uptake capacity (q_max) was 11.6 and 16.7?mg.g^?1 for Cd (II) and Ni (II), respectively. The biosorbent was characterised using Fourier transform infrared spectrometry (FTIR), scanning electron microscope (SEM), and energy-dispersive X-ray spectroscopy (EDX). The infrared spectrum demonstrated that hydroxyl, carboxyl, and phenolic functional groups are the major binding sites for Cd (II) and Ni (II) metals. The ion exchange mechanism plays an important role during biosorption process as shown in EDX analysis. Our results conclude that marine macrophyte C. nodosa can be used as a low-cost biosorbent for the removal of Cd (II) and Ni (II) in wastewater.     

Multivariate optimization of Cd(II) biosorption onto Ulmus tree leaves from aqueous waste

Ulmus tree leaves were successfully used as a novel and efficient biosorbent for removing cadmium, (Cd(II)), from aqueous solutions in a batch system. A multivariate strategy for optimization of removal efficiency conditions of Cd(II) was carried out. A 2³ full factorial design with three center points (9 runs) was performed for screening the main variables and reducing the large number of experimental runs. Initial concentration of metal ion (C _m), amount of sorbent (m), and pH were considered as the three main variables at two different levels. The maximum removal efficiency of Cd(II) was achieved within 1 h contact time. It was found that all the main factors and their interactions were significant at p < 0.05. Doehlert response surface methodology was utilized (13 runs) for finding a suitable mathematical model. The analysis of variance and some statistical tests such as lack-of-fit, coefficient of determination (R ²), and residual distribution plot confirmed the validity of the model. The optimum conditions for maximum removal of Cd(II) by Ulmus tree leaves were found as pH = 3.4, m (amount of sorbent) = 0.128 g, C _m (initial concentration of metal ion) = 12.1 mg L^?1.     

Kinetic studies of the degradation of parabens in aqueous solution by ozone oxidation

Ozone degradation of a mixture containing methylparaben, ethylparaben, propylparaben, butylparaben and benzylparaben was carried out in aqueous solution. The degradation followed the pseudo-first-order kinetic model and occurs with two ozonation stages with the observed rate constants of second stage ozonation, k _obs2, being higher than the observed rate constants in first stage, k _obs1. The k _obs1 of parabens was found to increase exponentially whilst k _obs2 was found to maximize at 35°C. Both k _obs1 and k _obs2 were found to decrease exponentially with respect to the initial concentration of parabens. Both pH and ozone dose showed positive effects on the rate of degradation. It was also observed that an ozone dose of 0.67 g/h resulted in the removal of 99% of parabens in 12 min, and also the removal of 61 and 32% of chemical oxygen demand (COD) and total organic carbon (TOC), respectively, in 3 h of ozonation time for a 500 μM of solution of parabens.     

海河流域沉积物中典型重金属的生态风险评估及验证

沉积物重金属污染及其生态风险评估日益受到关注,而沉积物质量基准是开展生态风险评估的有力工具。本研究通过物种敏感度分布法(species sensitivity distributions, SSD)和急慢性毒性比(acute to chronic ratios, ACR)推导了镍、铜、锌、镉和铅的沉积物质量基准(sediment quality guideline, SQG)。在获得合理的重金属沉积物慢性毒性数据的基础上,采用S-Logistic模型拟合镍、铜、镉和铅的慢性SSD曲线,采用S-Gompertz模型拟合锌的慢性SSD曲线。得到镍、铜、锌、镉和铅沉积物质量基准低值(sediment quality guideline low value, SQGlow)分别为18.6、69.9、107、1.26和38.4 mg·kg~(-1),应用ACRs,得到相应的沉积物质量基准高值(sediment quality guideline high value, SQGhigh)分别为167、226、556、10.1和384 mg·kg~(-1)。与加拿大和澳大利亚重金属沉积物基准值具有一定的可比性。选择花翅摇蚊(Chironomus kiiensis)、伸展摇蚊(Chironomus tentans)和霍甫水丝蚓(Limnodrilus hoffmeisteri)3种底栖生物作为受试生物,验证基准值对海河流域沉积物重金属毒性的预测能力。结果表明,利用SQGs预测沉积物毒性的总准确率为76.2%,3种底栖生物验证准确率从高至低为:花翅摇蚊>伸展摇蚊>霍甫水丝蚓。