Kinetic studies of adsorption of thiocyanate onto ZnCl2 activated carbon from coir pith, an agricultural solid waste

The adsorption of thiocyanate onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of various parameters such as agitation time, thiocyanate concentration, adsorbent dose, pH and temperature has been studied. Adsorption followed second-order rate kinetics. Two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q₀) was found to be 16.2 mg g⁻¹ of the adsorbent. The per cent adsorption was maximum in the pH range 3.0–7.0. pH effect and desorption studies showed that ion exchange and chemisorption mechanism are involved in the adsorption process. Thermodynamic parameters such as ΔG⁰, ΔH⁰ and ΔS⁰ for the adsorption were evaluated. The negative values of ΔH⁰ confirm the exothermic nature of adsorption. Effects of foreign ions on the adsorption of thiocyanate have been investigated. Removal of thiocyanate from ground water was also tested.     

Cold season CH4, CO2 and N2O fluxes from freshwater marshes in northeast China

Cold season (winter and thaw) CH₄, CO₂ and N₂O fluxes from freshwater marshes (47°35′N, 133°31′E, Northeast China) were measured, using the static chamber method. The mean CH₄ and CO₂ fluxes from Carex lasiocarpa (Cl) were 0.5 ± 0.19 and 6.23 ± 1.36 mg C m⁻² h⁻¹, respectively, and those from Deyeuxia angustifoli (Da) were 0.18 ± 0.15 and 5.22 ± 2.48 mg C m⁻² h⁻¹, respectively in winter. There was no significant difference between Cl and Da (p > 0.05). The contributions of winter CH₄ fluxes were about 5.5% and 3% in the Cl and Da, respectively. Marshes are an important potential N₂O sink in winter season in northeast China. During thaw, the CH₄ and CO₂ emissions rapidly increased, 4.5–6 times of winter emissions. Wetland became a source of N₂O. Cold season gases flux from northern wetlands play an important role in the seasonal gas exchange.     

Photochemical oxidation of reduced sulfur compounds in an urban location based on short time monitoring data

This study examines the oxidation of reduced sulfur compounds (RSCs) in urban ambient air. The photochemical conversions of RSC (such as DMS, CS₂, H₂S, DMDS, and CH₃SH) to a further oxidized form (e.g., SO₂, MSA, and H₂SO₄) were assessed using a photochemical box model. For our model simulation of RSC oxidation, measurements were taken at an urban monitoring station in Seoul, Korea (37.6° N, 127° E) during three separate time periods (e.g., Sept. 17–18, Oct. 23, and Oct. 27–28, 2003). The results indicate that DMS and H₂S were the dominant RSCs with concentrations of 370 ± 140 and 110 ± 60 pptv, respectively. The photochemical conversion of DMDS to SO₂ was found to occur more efficiently than other RSCs. The overall results of our study suggest that photochemical conversion of RSCs accounted for less than 15% of the observed SO₂ during the measurement period. The SO₂ production from DMS oxidation (mainly by the reaction with OH) was found to be affected primarily by the abstraction channel due to high NO_x levels during the experimental conditions.     

Photocatalytic activity of the calcined H-titanate nanowires for photocatalytic oxidation of acetone in air

Hydrogen titanate (H-titanate) nanowires were prepared via a hydrothermal reaction of TiO₂ powders (P25) in KOH solutions and then calcined at various temperatures. The phase structure, crystallite size, morphology, specific surface area, and pore structures of the calcined H-titanate nanowires at various temperatures were characterized with field emission scanning electron microscope, X-ray diffraction, transmission electron microscopy and nitrogen adsorption–desorption isotherms, and their photocatalytic activities were evaluated by photocatalytic oxidation of acetone in air. With increasing calcination temperature, the specific surface area and porosity of the calcined samples steadily decreased. At a calcination temperature range of 400–600 °C, the calcined H-titanate nanowires showed higher photocatalytic activity than P25 powders for photocatalytic oxidation of acetone. Especially, at 500 °C, the calcined H-titanate nanowires showed the highest photocatalytic activity, which exceeded that of P25 by a factor of about 1.8 times. This can be attributed to the synergetic effect of larger specific surface area, higher pore volume and the presence of brookite TiO₂. With further increase in the calcination temperature (700–900 °C), the photocatalytic activity of the samples decreased obviously owing to the growth of TiO₂ crystallites.     

Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

Removal of a cationic dye from aqueous solutions by adsorption onto bentonite clay

The ability of bentonite to remove malachite green from aqueous solutions has been studied for different adsorbate concentrations by varying the amount of adsorbent, temperature, pH and shaking time. Maximum adsorption of the dye, i.e. >90% has been achieved in aqueous solutions using 0.05 g of bentonite at a pH of 9. Thermodynamic parameters such as ΔH°, ΔS° and ΔG° were calculated from the slope and intercept of the linear plots of ln K_D against 1/T. Analysis of adsorption results obtained at 298, 308, 318 and 328 K showed that the adsorption pattern on bentonite seems to follow the Langmuir, Freundlih and D–R isotherms. The temperature increase reduces adsorption capacity by bentonite, due to the enhancement of the desorption step in the mechanism. The numerical values of sorption free energy (E_a) of 1.00–1.12 kJ mol⁻¹ indicated physical adsorption. The kinetic data indicated an intraparticle diffusion process with sorption being first order. The rate constant k was 0.526 min⁻¹. The concentration of malachite green oxalate was measured before and after adsorption by using UV–Vis spectrophotometer.     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 1-aliphatic hydrocarbons

The temporal variability and bioaccumulation dynamics of C_12–25 n-alkanes, isoprenoids and unresolved aliphatic hydrocarbons (UCM) were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the sewage impacted Buenos Aires coastal area. Fish muscles contain huge amounts of n-C_12–25 (165 ± 93, 70 ± 48 or 280 ± 134 μg g⁻¹, dry, fresh and lipid weight, respectively) and UCM (931 ± 560, 399 ± 288 and 1567 ± 802 μg g⁻¹) reflecting the chronic bioaccumulation of fossil fuels from sewage particulates. On a temporal basis, lipid normalized aliphatic concentrations peaked by the end of 2001–2002 during the rainiest period over the last four decades (1750 vs. 1083 ± 4.6 mm in 1999, 2004 and 2005), reflecting an enhanced exposition due to massive anthropogenic fluxes from Metropolitan Buenos Aires in wet years. The hydrocarbon composition in fish muscles is enriched in n-C_15–17 and isoprenoids relative to a fresh crude oil and settling particulates, with fresher signatures during the 2001–2002 maxima. Fish/settling material bioaccumulation factors (BAFs: 0.4–6.4 dry weight or 0.07–0.94 lipid-organic carbon) plotted against K_ow showed a parabolic pattern maximizing at n-C_14–18 and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log K_ow: 7.2–9.9), intermediate-size C_14–18 n-alkanes and C_15–20 isoprenoids (MW: 198–282; length: 17.9 to 25.4 Å) with melting points ranging from −19.8 to 28 °C. The uptake efficiency is inversely correlated to melting points and increased from 75% for n-C₂₅ to above 90% for n-C_14–15 and isoprenoids.     

Electrochemical determination of anaerobic microbial decay coefficients

The biokinetics of attached and suspended bacteria are an essential component of activated sludge models, anaerobic digestion models and biofilm models. These parameters are often assumed or “confirmed” based on the goodness-of-fit of the bioprocess models. Using a microbial fuel cell with a baffled reactor chamber, the attached- and mixed-growth microbial decay coefficients were evaluated under anaerobic conditions. The capability for real-time voltage recording allows easy and accurate measurement of the anaerobic microbial decay coefficients (b_L, lysis-regrowth approach), which were determined to be 0.11 ± 0.01 and 0.15 ± 0.01 d⁻¹ for attached (to anode) and mixed (present in the anode chamber) growth microorganisms, respectively. The corresponding half-saturation constants using glucose as a substrate were 204 ± 10 and 123 ± 1 mg COD l⁻¹. Hence, like an oxygen uptake rate-based approach to measure the microbial kinetics under aerobic conditions, the electrochemical recording provides an attractive method to measure anaerobic microbial decay coefficients.     

Determination of dithiocarbamate fungicide propineb and its main metabolite propylenethiourea in airborne samples

A simple, rapid and sensitive GC–MS method for the determination of dithiocarbamate fungicide propineb [polymeric zinc propylenebis (dithiocarbamate)] and an improved HPLC procedure for the simultaneous determination of its main metabolite, propylenethiourea, and ethylenethiourea, the main metabolite of all ethylenedithiocarbamates, in airborne samples are described. The method for the analysis of propineb involves the evolution of carbon disulfide (CS₂), under acidic conditions in the presence of stannous chloride, extraction of the generated CS₂ into a layer of isooctane which is then analyzed for CS₂ content by GC–MS in SIM mode. Under the optimum conditions, the retention time of CS₂ was 1.89 min and the total time of chromatographic analysis was 5 min. Recoveries from spiking glass microfibre filters (GF/A) and silica gel filters were 86 ± 7 (n = 9) and 89 ± 4 (n = 9), respectively. The limit of detection is 0.7 ng per filter, which is equivalent to about 0.8–1.0 ng m⁻³ in air. In parallel, an HPLC method with ultraviolet detection is presented for the simultaneous analysis of the metabolites. Separation of the two metabolites was attained in less than 5 min. Recoveries from spiking GF/A and silica gel filters for ethylenethiourea were 100 ± 1 (n = 3) and 98 ± 2 (n = 3), respectively, while for propylenethiourea were 102 ± 1 (n = 3) and 98 ± 1 (n = 3), respectively. The detection limits are about 36–43 and 40–49 ng m⁻³ in air for ethylenethiourea and propylenethiourea, respectively. All the analytes spiked in the filters are proven to be stable for more than one month, at −4 °C.     

Decomposition of chlorinated dioxins, odourous compounds and NOx from MSW incineraton plant by oxidizing catalyst

An experiment was carried out to decompose chlorinated dioxins (PCDDs, PCDFs) Chlorobenzenes, NOx and odourous compounds (H₂S, CH₄S, C₂H₆S₂, C₈H₈, C₂H₆S, C₂H₄O, NH₃) simultaneously using a catalyst in the MSW incineration plant. The experiments were conducted at temperatures from 200°C to 400°C and from 3000h⁻¹ to 6000h⁻¹ at space velocity. A catalyst containing V₂O₅ and WO₃ on the basis of TiO₂ is used, an oxidizing catalyst of the honeycomb type. The average decomposition efficiencis were 95%, 98%, 92% for PCDDs(48CDDs), PCDFs(48CDFs) and Chlorobenzenes(36CLBs) at a reaction temperature of 350°C and a space velocity of 3000h⁻¹, more than 90% for NOx at a reactiont temperature of 300°C and more than 80% for odourous compounds at the reaction temperature of 300°C and a space velocity of 6000h⁻¹. All those compounds were decomposed successfully with increasing contact time and surface. The rate-determing step was the chemical reaction of catalyst surface.     

Leaching of atrazine, metolachlor and diuron in the field in relation to their injection depth into a silt loam soil

A field experiment was conducted on a Calcaric Cambisol soil to study the consequences of the penetration depth and properties of pesticides on the risk of subsequent leaching. Three pesticides with different mobility characteristics and bromide were injected at 30 cm (where soil organic matter (OM) was 2%) and 80 cm (soil OM 0.5%) on irrigated plots without a crop. The migration of injected solutes was assessed for two years by sampling the soil solution using six porous cups installed at 50 and 150 cm depth and by relating solute contents to drainage water flux estimated by the STICS model (Simulateur mulTIdisciplinaire pour les Cultures Standard). Pesticides injected at 30 cm were strongly retained so that no metolachlor or diuron was detected at 50 and 150 cm. The ratio of atrazine peak concentration in the soil solution to concentration in the injected solution (C/C₀) was 1 × 10⁻³ and 0.2 × 10⁻³, respectively, at 50 and 150 cm. When injected at 80 cm, (C/C₀) of atrazine, metolachlor and diuron were 10 × 10⁻³, 1 × 10⁻³ and 0.3 × 10⁻³ at 150 cm, respectively; 1/(C/C₀) was correlated with K_oc values reported from databases. The ratio of drainage volume to the amount of water at field capacity in the soil layer between the injection point at 30 cm and the water sampling level (V/V₀) at 50 and 150 cm was 0.6 and 0.9, respectively, for bromide and 1.6 and 1.0 for atrazine. V/V₀ of the injected solutes at 80 cm was for bromide, atrazine, metolachlor and diuron 0.6, 0.9, 1.2 and 1.7, respectively; pesticide V/V₀ was correlated with K_oc. The retardation factor was a good indicator of migration risk, but tended to overestimate retardation of molecules with high K_oc. Atrazine desorption represented an additional leaching risk as a source of prolonged low contamination. The large variability in soil solution of bromide and pesticide concentrations in the horizontal plane was attributed to flow paths and clods in the tilled soil layer. This heterogeneity was assumed to channel water fluxes into restricted areas and thereby increase the risk of groundwater contamination. The methodology used in the field proves to provide consistent results.     

Microwave-induced combustion of volatile organic compounds in an industrial flue gas over the magnetite fixed-bed

A modified domestic microwave oven was applied to heat a magnetite (Fe₃O₄) fixed-bed for continuous decomposition of volatile organic compounds (VOCs), such as acetone, n-hexane, and dichloromethane (DCM), in a simulated flue gas which contains VOCs equivalent to 2000 ppmv as DCM. Experimental results revealed that effect of the addition of water to the inlet stream on decomposition of DCM in the overall experiment was insignificant. Bulk temperature of the Fe₃O₄ fixed-bed was also found to reach 600 °C from an initial room temperature by 6.5 min under microwave radiation, even though the inlet gas was at a high gas hourly space velocity of 5240 h⁻¹ and a high relative humidity of 75%. Moreover, the VOCs in the inlet stream could be decomposed completely over the Fe₃O₄ fixed-bed by microwave heating at a power level of 645 W at heating time of 10 min. The conversion of VOCs is stable when the Fe₃O₄ fixed-bed has been heated longer than 10 min with microwave radiation. The microwave-induced heating upon Fe₃O₄ fixed-bed processing appears to be not only an energy efficient technique for air pollutions treatment but also a promising technology for variety of VOCs in a flue gas from industrial factory being decomposed simultaneously and completely.     

High infrared radiance glass-ceramics obtained from fly ash and titanium slag

A new glass–ceramic was synthesized by crystal growth from a homogenous glass obtained by melting a mixture of fly ash collected from a power plant in Hebei province of China, titanium slag collected from a titanium factory in Sichuan province of China, and MgCO₃ as an additive. According to the measurement results of differential thermal analysis, a thermal treatment of nucleating at 850 °C for 2 h and crystallizing at 985 °C for 1.5 h was used to obtain the crystallized glass. X-ray diffraction and scanning electron microscopy measurements showed that the main crystalline phase of this material was iron-ion substituted cordierite, (Mg,Fe)₂Al₄Si₅O₁₈, which is homogeneously dispersed within the parent glass matrix. The infrared radiance and thermal expansion coefficient of this material have been examined, and the results demonstrate that this glass–ceramic material has potential for application in a wide range of infrared heating and drying materials.     

Removal of carbon disulfide via coupled reactions on a bi-functional catalyst: experimental and modeling results

A mathematical model describing the rate of carbon disulfide (CS₂) removal due to coupled reactions has been developed. Kinetic studies were carried out in a fixed bed reactor under atmospheric pressure and a range of temperatures (85–125 °C). The effects of flow rate, CS₂ inlet concentration, temperature and relative humidity were analyzed. A kinetic model based on axial dispersion, external and internal mass-transfer resistances, as well as effects of S deposition on the inner-face of the catalyst was in agreement with the CS₂ experimental breakthrough curves. The mathematical model can be used for process design and scale up of similar systems.     

Sorption behavior of a new acidic herbicide in soils

The sorptive behavior of the experimental herbicide quinmerac (7-chloro-3-methyl-quinoline-8-carboxylic acid) was investigated in soils of different organic carbon content. Distribution coefficients are low (K_d = 0.03 - 12 mL g⁻¹) and are mainly determined by the soil organic carbon content. The adsorption mechanism operating in neutral to slightly acid agricultural soils is supposed to be cation bridging with the anionic form of quinmerac. Under acid conditions (pH 5.2) the predominating sorption mechanism is hydrophobic interaction. Therefore soil pH and cationic composition are also major factors determining the sorptive capacity of soils for quinmerac.

Adsorption kinetics, equilibrium adsorption and desorption isotherms were determined in batch experiments. Sorption kinetics were investigated at various times from 15 min to 96 hours. A two-step sorption behavior with time was found for the anionic form indicating two types of sorption mechanisms or sorption sites. Equilibrium for the first type was reached at a time-scale of minutes and for the second type after 24 hours. Adsorption isotherms were determined for two soil/solution ratios 1/5 and 1/3. Alteration of the adsorbent concentration exerted a strong influence on the adsorption isotherms. An increase of sorption was found with increasing adsorbent concentration. Under natural soil conditions sorption is therefore expected to be higher compared to the batch experiments. Desorption isotherms were obtained using the consecutive desorption method. Desorption hysteresis was not observed which indicates weak interactions. Implications of the results for the movement of quinmerac under field conditions and for models describing transport are discussed.     

Biogeochemical distinction of methane releases from two Amazon hydroreservoirs

Biogeochemical distinction of methane emissions to the atmosphere may essentially rely on the surface area and morphometry of Amazon hydroreservoirs. Tucuruí (deep) and Samuel (shallow) reservoirs released in average 13.82 ± 22.94 and 71.19 ± 107.4 mg CH₄ m⁻² d⁻¹, respectively. δ¹³C–CH₄ values from the sediments to the atmosphere indicate that the deep reservoir has extended methanotrophic layer, oxidizing large quantities of light isotope methane coming from the sediments, while sediment-generated methane can easily evade the shallow reservoir.     

Formation of chloroarenes upon gas-phase pyrolysis and slow combustion of benzene-HCl mixtures

Pyrolysis (800–900°C, ca. 5 s) of benzene/HC1 mixtures leads to chlorobenzene (1) even in a reducing environment of H₂ and/or CH₄. With added oxygen, 1 is formed even at 550°C; such slow combustions also yield chlorinated phenols and dibenzofurans.     

Mercury in air in an area impacted by strong industrial activities

The concentrations of total gaseous mercury (TGM) and its relevant environmental parameters were measured at a highly industrialized area in the Ban Wall industrial complex (BWIC) in An San city, Korea from March to May 2005. The mean concentrations of Hg measured during the entire study period were computed to be 6.32 ± 8.56 ng m⁻³ (range of 2.32–181 ng m⁻³; N = 1160). Due to the effects of strong man-made activities, the significantly high Hg concentration levels (e.g., at or above 10 ng m⁻³) comprised about 7.5% of all data with the mean of 21.8 ± 26.3 ng m⁻³ (N = 87). By separating the data into daytime and nighttime periods, the Hg values exhibited a notable daytime enhancement possibly due to strong man-made activities during working hours. The results of the correlation analysis indicated the possible relationship between the Hg concentration and the temperature as well as several pollutant species (e.g., NO₂ and NO_x). Evaluation of the Hg data in relation with the air mass transport pattern confirms that the Hg concentration levels in this industrial area are affected most eminently by local, rather than distant, pollution sources.     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.