Adsorption and catalytic decomposition of methyl bromide and methyl iodide on activated carbons

Methyl bromide (MeBr) is commonly used for fumigating structures and commodities. Emission of MeBr during such treatments is environmentally detrimental because of the reaction of MeBr with stratospheric ozone. In this study we evaluated adsorption of MeBr and methyl iodide (MeI) – a potential MeBr replacement, on five commercial activated carbons, and studied water-initiated catalytic decomposition of adsorbed fumigants. All carbon samples showed great adsorption affinity to MeBr and MeI, with the adsorption capacity for MeI several times greater than that for MeBr on the same carbon. For the same fumigant, adsorption was affected by the type of carbon and the concentration of fumigant. Water initiated decomposition of both fumigants, liberating Br⁻ or I⁻ as a transformation product. The rate of decomposition increased with increasing temperature, and was also influenced by the carbon type. The half-life of MeBr or MeI on Centaur, a catalytically modified carbon, was <2 h at 80°C. The rapid decomposition of MeBr and MeI on wet carbons at elevated temperatures may be used to detoxify these fumigants after adsorption on activated carbons.     

Determination of group parameters for organically bound chlorine, bromine and iodine in precipitation

The presence of organically bound halogens in precipitation was studied by first adsorbing organics on activated carbon and then analysing the chloride, bromide and iodide formed during combustion of the carbon. A standard instrument for the group parameter AOX (adsorbable organic halogens) was used for the combustion. The halides formed were trapped in an alkaline solution and analysed by capillary zone electrophoresis. The method described enabled determination of sub-ppb concentrations of the group parameters AOCl, AOBr and AOI (adsorbable organic chlorine, bromine and iodine, respectively). Analysis of rain and snow collected at different sites in Europe showed that organochlorines were responsible for the major part of the AOX content in all samples collected. Organically bound bromine was found in sub-ppb concentrations in all of the samples, whereas organic iodine was detected in only two of the samples.     

Prediction of the adsorption capability onto activated carbon of a large data set of chemicals by local lazy regression method

Accurate quantitative structure–property relationship (QSPR) models based on a large data set containing a total of 3483 organic compounds were developed to predict chemicals’ adsorption capability onto activated carbon in gas phrase. Both global multiple linear regression (MLR) method and local lazy regression (LLR) method were used to develop QSPR models. The results proved that LLR has prediction accuracy 10% higher than that of MLR model. By applying LLR method we can predict the test set (787 compounds) with Q²_ext of 0.900 and root mean square error (RMSE) of 0.129. The accurate model based on this large data set could be useful to predict adsorption property of new compounds since such model covers a highly diverse structural space.     

Selection and Substantiation of an Organic Solvent Removal Apparatus at a Print Shop by Comparative Experiments Using the Activated Carbon Adsorption and Catalytic Oxidation Methods

ABSTRACT

The investigation of an appropriate organic solvent removal apparatus for installation in a newly reconstructed print shop as a countermeasure for preventing the exhaust of organic solvents was conducted.

The selection of an organic solvent removal apparatus was made after bench-scale tests of the activated carbon adsorption method and the catalytic oxidation method, both of which are effective for the removal of organic solvents, were performed on the actual exhaust gas at the print shop. The results showed that both methods were efficient enough to be applied to the removal of organic solvents, but the activated carbon adsorption method had many drawbacks, such as the need for frequent replacement of activated carbon and complex maintenance. For the catalytic oxidation method, running costs are high, but there are many merits, such as that the catalysts do not have to be replaced as often and maintenance is simple. After considering these factors, a catalytic oxidation removal apparatus was installed at the new print shop. In the results of the substantiation test on the actual apparatus using mixed catalysts of platinum and manganese plus copper, the removal efficiency was 97.998.7% and the concentration of the outlet exhaust gas was about 10 ppm (the average concentration of the inlet exhaust gas was 528 ppm) at a space velocity of 30,000 hr^-1 and a reaction temperature of 200 °C. The results of this study were substantiated.     

Physicochemical characteristics of carbonaceous adsorbent for dioxin-like polychlorinated biphenyl adsorption

It has been known that dioxin-like polychlorinated biphenyls (DL-PCBs) are present in almost all types of environments worldwide. Activated carbon treatment has been expected for the removal of DL-PCBs because it is a simple and low-cost removal technology. In the present study, the physicochemical properties of activated carbon were investigated to identify the characteristics of 16 different types of activated carbon on adsorption properties for DL-PCBs. To accomplish this, micropore volume, and pore diameter were calculated by t-plot analysis and the mesopore volume was analyzed by the Barrett-Joyner-Halenda (BJH) method. In addition, the Brunauer-Emmett-Teller (BET) surface area, pH, metal elements, and surface acid functional groups were analyzed. Then, adsorption experiments using DL-PCB in hexane solution were conducted, and the relationship between adsorption and physicochemical properties of activated carbon was investigated. The results showed that activated carbons having a surface area of 700-1200 m² g⁻¹ and micropores with diameters of about 0.7-0.8 nm exhibited high activity for the adsorption of PCBs. The results also clearly showed that the mesopore volume of activated carbon influenced the adsorption rate and the equilibrium adsorption.     

Organic acids in springtime wisconsin precipitation samples

A short-term study on organic acids in precipitation was conducted from 15 March to 1 June 1984 at two sites on the Wisconsin Acid Deposition Monitoring Network. Aliquots of collected samples were fixed with tetrachloromercurate (TCM) and analyzed for low molecular weight organic anions via ion-exclusion chromatography (ICE). Unfixed aliquots were subjected to standard network inorganic analyses. Of the 31 samples collected, 30 contained detectable concentrations of formate and acetate ions, with concentrations ranging from < 0.43 to 56μmol ℓ⁻¹ for the former and < 0.83 to 33 μmol ℓ⁻¹ for the latter. Propionate, oxalate and malonate ions were also detected in a number of samples. Statistical analysis of the combined organic and inorganic data set indicated that no significant differences existed between the concentrations of organic ions at the two sites; however, samples containing visible sediments had significantly greater concentrations than samples without sediments. Maximum contributions of the organic acids to precipitation-free acidity, calculated by assuming that the only sources of the measured formate and acetate were their respective acid forms, averaged 18.6% for samples with a pH ⩽ 5.0. Formate and acetate concentrations were highly correlated. Correlations between organic and inorganic ions were weak; NH⁺₄ and Ca²⁺ generally exhibited the highest, though still weak, correlations. The study emphasizes the need for further, longer-term investigations to determine the role of low molecular weight organic compounds in precipitation chemistry.     

Production of sugarcane bagasse-based activated carbon for formaldehyde gas removal from potted plants exposure chamber

Agricultural wastes such as rice straw, sugar beet, and sugarcane bagasse have become a critical environmental issue due to growing agriculture demand. This study aimed to investigate the valorization possibility of sugarcane bagasse waste for activated carbon preparation. It also aimed to fully characterize the prepared activated carbon (BET surface area) via scanning electron microscope (SEM) and in terms of surface functional groups to give a basic understanding of its structure and to study the adsorption capacity of the sugarcane bagasse-based activated carbon using aqueous methylene blue (MB). The second main objective was to evaluate the performance of sugarcane bagasse-based activated carbon for indoor volatile organic compounds removal using the formaldehyde gas (HCHO) as reference model in two potted plants chambers. The first chamber was labeled the polluted chamber (containing formaldehyde gas without activated carbon) and the second was taken as the treated chamber (containing formaldehyde gas with activated carbon). The results indicated that the sugarcane bagasse-based activated carbon has a moderate BET surface area (557 m²/g) with total mesoporous volume and microporous volume of 0.310 and 0.273 cm³/g, respectively. The prepared activated carbon had remarkable adsorption capacity for MB. Formaldehyde removal rate was then found to be more than 67% in the treated chamber with the sugarcane bagasse-based activated carbon. The plants’ responses for this application as dry weight, chlorophyll contents, and protein concentration were also investigated.

Implications: Preparation of activated carbon from sugarcane bagasse (SCBAC) is a promising approach to produce cheap and efficient adsorbent for gas pollutants removal. It may be also a solution for the agricultural wastes problems in big cities, particularly in Egypt. MB adsorption tests suggest that the SCBAC have high adsorption capacity. Formaldehyde gas removal in the plant chambers indicates that the SCBAC have potential to recover volatile gases. The results confirmed that the activated carbon produced from sugarcane bagasse waste raw materials can be used as an applicable adsorbent for treating a variety of gas pollutants from the indoor environment.     

Dissolved organic carbon in rainwater: Glassware decontamination and sample preservation and volatile organic carbon

The efficiency of different methods for the decontamination of glassware used for the analysis of dissolved organic carbon (DOC) was tested using reported procedures as well as new ones proposed in this work. A Fenton solution bath (1.0 mmol L⁻¹ Fe²⁺ and 100 mmol L⁻¹ H₂O₂) for 1 h or for 30 min employing UV irradiation showed to combine simplicity, low cost and high efficiency. Using the optimized cleaning procedure, the DOC for stored UV-irradiated ultra-pure water reached concentrations below the limit of detection (0.19 μmol C L⁻¹). Filtered (0.7 μm) rain samples maintained the DOC integrity for at least 7 days when stored at 4 °C. The volatile organic carbon (VOC) fraction in the rain samples collected at two sites in São Paulo state (Brazil) ranged from 0% to 56% of their total DOC content. Although these high-VOC concentrations may be derived from the large use of ethanol fuel in Brazil, our results showed that when using the high-temperature catalytic oxidation technique, it is essential to measure DOC rather than non-purgeble organic carbon to estimate organic carbon, since rainwater composition can be quite variable, both geographically and temporally.     

活性炭吸附和脱附-等离子体氧化净化有机废气的研究

根据滑动弧放电等离子体适于降解高浓度有机物废气的特性,结合活性炭吸附法,提出了吸附器的吸附浓缩和热脱附-等离子体氧化净化有机废气的方法。在活性炭吸附过程中,最初2 h内甲苯净化率达到100%,随着时间的增加净化率下降;在热脱附滑动弧放电等离子体净化过程中,甲苯降解效率最高为97.3%。将滑动弧放电等离子体反应器出口气相产物收集进行FT-IR检测,发现放电后有CO2、CO、H2O和NO2产生,并分析了甲苯的降解机理。     

Dynamic NO adsorption characteristics of iron-treated activated carbon fibers

The breakthrough curve for NO adsorption on the activated carbon fibers treated in iron salt solutions was determined. They can adsorb much more NO than granular activated carbon by a factor of more than 10 from a flowing 300 ppm NO-N₂ mixed gas at 100°C and 20 ml min⁻¹; the most effective one of the iron-treated carbon fibers of 0.2 g is able to reduce the NO concentration from 300 ppm to 30 ppm. These adsorbents can adsorb the same amount of NO from even a 300 ppm NO-500 ppm SO₂-10% CO₂-10% H₂O-1% O₂-N₂ mixed gas.     

浸渍-碱性微波法载磁活性炭粉对壬基酚的吸附

利用浸渍-碱性微波法制备载磁粉末活性炭,通过等温吸附实验和动力学吸附实验,研究对比了其与原料活性炭、浸渍载铁活性炭对壬基酚的吸附性能。采用氮气吸附仪、FTIR、XRD、国标(GB/T12496.19-1999)邻菲啰啉分光度法及VSM,分别对3种样品进行了物相结构、表面官能团、铁含量及磁性能的分析,并探讨了吸附机理。结果表明,浸渍-碱性微波法载磁活性炭的总孔容及孔隙率均有较大提高;其吸附等温线符合Freundich方程,吸附动力学过程符合准二级动力学方程与孔道内扩散模型,相关系数R2均大于0.900。原活性炭经一定浓度的铁盐溶液浸渍后,铁含量由2%提高到8%。在碱性、N2气氛条件下微波后,铁系物主要存在形式为零价铁和Fe3O4,制得的载磁活性炭饱和磁化强度为1.12 emu/g。     

微型舱模拟室内环境中活性炭净化甲醛的能力

利用微型实验舱(0.04 m3)模拟室内甲醛环境进行活性炭吸附实验,研究吸附后甲醛浓度随时间的变化趋势,计算活性炭对甲醛的净化效率、吸附速率和饱和吸附量,探索活性炭对室内甲醛的吸附规律.研究发现,当甲醛含量为0 ～0.40 mg,活性炭用量为0.5g时,舱内甲醛浓度随时间延长呈指数递减变化趋势,吸附后0～0.5 h甲醛浓度递减得最快,0.5～2h递减速度变缓,2～4h甲醛浓度基本上保持不变;研究E0A1、E1A4曲线斜率K及活性炭甲醛净化效率发现,每次吸附过程活性炭吸附2h可达到吸附平衡,活性炭进行3次吸附平衡即可达到吸附饱和,每次实验第一次吸附过程、每次吸附过程前半小时活性炭对甲醛的吸附能力最强;活性炭的吸附速率在吸附初期迅速降低,最后趋近于0;等量椰壳活性炭在一定浓度的污染物环境中饱和吸附量是个定值.说明使用活性炭净化室内甲醛有一定的规律可循.     

Organic contaminates in water

Abstract

The carbon adsorption method was used for separating organic matter from large samples of drainage, river and tap water. The carbon chloroform extract (CCE) was separated into different solubility fractions and the neutral fraction was separated into aliphatic, aromatic and oxy‐compounds using column chromatography. The aromatic fraction was subjected to TLC, IR and UV analysis. The pesticide endrin was present in both river and tap water at concentrations of 0.7 and 1.5 ppb, respectively.     

Fractionation of halogenated organic matter present in rain and snow

Organic matter in samples of rain and snow from Sweden, Poland, Germany and the Republic of Ireland was fractionated by employing a series of filtration, purging, evaporation and extraction steps. Determinations of the group parameter AOX (adsorbable organic halogens) in aqueous phases and EOX (extractable organic halogens) in organic phases showed that halogenated organic matter present in bulk precipitation is composed of several different groups of compounds. The largest amounts of organically bound halogens were found in fractions of relatively polar and non-volatile to semivolatile compounds. In particular, a significant part of the AOX could be attributed to alkaline-labile organic bases. Gas chromatographic analysis of different organic extracts in the chlorine channel of an atomic emission detector (AED) resulted in chromatograms with few distinct peaks, and analysis in the bromine channel did not produce any distinct peaks. Chlorinated acetic acids were the most abundant halogenated organic acids, and chlorinated alkyl phosphates were normally responsible for the largest peaks in the chlorine chromatogram of neutral, hexane-extractable compounds. When analysing volatiles, 1,4-dichlorobenzene and a thus far unidentified chloroorganic compound often caused the largest response in the chlorine channel of the AED system.     

Properties of organic matter in PM2.5 at Changdao Island,China—A rural site in the transport path of the Asian continental outflow

Fifty-five seasonal PM_2.5 samples were collected March 2003–January 2004 at Changdao, a resort island located at the demarcation line between Bohai Sea and Yellow Sea in Northern China. Changdao is in the transport path of the continental aerosols heading toward the Pacific Ocean in winter and spring due to the East Asia Monsoon. Solvent-extractable organic compounds (SEOC), organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) were analyzed for source identification based on molecular markers. This data set provides useful information for the downstream site researchers of the Asian continental outflow. Total carbon (TC, OC+EC) was ∼18 μg m⁻³ in winter, ∼9 μg m⁻³ in spring and autumn and a large part of the TC was WSOC (33% in winter, >45% in the other seasons). Winter and spring were the high SEOC seasons with n-fatty acids the highest at ∼290 and ∼170 ng m⁻³, respectively, followed by n-alkanes at ∼210 and ∼90 ng m⁻³, and polycyclic aromatic hydrocarbons (PAHs) were also at high at ∼120 and ∼30 ng m⁻³. High WSOC/TC, low C_18:1/C₁₈ of fatty acids, and low concentrations of labile PAHs such as benzo(a)pyrene, together with back trajectory analysis suggested that the aerosols were aged and transported. PAHs, triterpane and sterane distributions provided evidence that coal burning was the main source of the continental outflow. The detection of levoglucosan and β-sitosterol in nearly all the samples showed the impact of biomass burning.     

改性污泥活性炭对水中镉离子的吸附性能

以城市污水处理厂的剩余污泥为原料,氯化锌为活化剂制备污泥活性炭,对一部分污泥活性炭用6.0 mol/L的硝酸进行改性,并研究了未改性和改性的污泥活性炭对Cd2＋的吸附行为的影响。结果表明,在pH为5.0、Cd2＋初始浓度为100 mg/L、吸附剂投加量为2.0 g/L、反应温度为25℃时,未改性的污泥活性炭吸附容量为8.45 mg/g,硝酸改性的污泥活性炭吸附容量达到了23.35 mg/g。改性和未改性的污泥活性炭对Cd2＋都有较好的吸附容量,硝酸改性大幅度提高了污泥活性炭对Cd2＋的吸附性能。常温下改性污泥活性炭对Cd2＋的吸附符合Langmuir吸附等温式。     

Removal of organic contaminants in bioretention medium amended with activated carbon from sewage sludge

Bioretention, also known as rain garden, allows stormwater to soak into the ground through a soil-based medium, leading to removal of particulate and dissolved pollutants and reduced peak flows. Although soil organic matter (SOM) is efficient at sorbing many pollutants, amending the bioretention medium with highly effective adsorbents has been proposed to optimize pollutant removal and extend bioretention lifetime. The aim of this research was to investigate whether soil amended with activated carbon produced from sewage sludge increases the efficiency to remove hydrophobic organic compounds frequently detected in stormwater, compared to non-amended soil. Three lab-scale columns (520 cm³) were packed with soil (bulk density 1.22 g/cm³); activated carbon (0.5% w/w) was added to two of the columns. During 28 days, synthetic stormwater—ultrapure water spiked with seven hydrophobic organic pollutants and dissolved organic matter in the form of humic acids—was passed through the column beds using upward flow (45 mm/h). Pollutant concentrations in effluent water (collected every 12 h) and polluted soils, as well as desorbed amounts of pollutants from soils were determined using GC-MS. Compared to SOM, the activated carbon exhibited a significantly higher adsorption capacity for tested pollutants. The amended soil was most efficient for removing moderately hydrophobic compounds (log K _ow 4.0–4.4): as little as 0.5% (w/w), carbon addition may extend bioretention medium lifetime by approximately 10–20 years before saturation of these pollutants occurs. The column tests also indicated that released SOM sorb onto activated carbon, which may lead to early saturation of sorption sites on the carbon surface. The desorption test revealed that the pollutants are generally strongly sorbed to the soil particles, indicating low bioavailability and limited biodegradation.

     

Formation potentials of bromate and brominated disinfection by-products in bromide-containing water by ozonation

The ozonation involved in drinking water treatment raises issues of water quality security when the raw water contains bromide (Br^?). Br^? ions may be converted to bromate (BrO₃ ^?) during ozonation and some brominated disinfection by-products (Br-DBPs) in the following chlorination. In this study, the effects of ozone (O₃) dosage, contact time, pH, and Br^? and ammonia (NH₃-N) concentrations on the formation of BrO₃ ^? and Br-DBPs have been investigated. The results show that decreasing the initial Br^? concentration is an effective means of controlling the formation of BrO₃ ^?. When the concentration of Br^? was lower than 100 μg/L, by keeping the ratio of O₃ dosage to dissolved organic carbon (DOC) concentration at less than 1, BrO₃ ^? production was effectively suppressed. The concentration of BrO₃ ^? steadily increased with increasing O₃ dosage at high Br^? concentration (>900 μg/L). Additionally, a longer ozonation time increased the concentrations of BrO₃ ^? and total organic bromine (TOBr), while it had less impact on the formation potentials of brominated trihalomethanes (Br-THMFP) and haloacetic acids (Br-HAAFP). Higher pH value and the presence of ammonia may lead to an increase in the formation potential of BrO₃ ^? and Br-DBPs.     

Determination of total particulate sulfur at Whiteface mountain,New York,by pyrolysis microcoulometry

Total paniculate sulfur (TPS) in air samples can be determined by a technique based on thermal volatilization at 1000°C, followed by controlled oxidation of sulfur compounds to SO₂ and coulometric titration of SO₂ with iodine. Calibration curves are linear within 5% from 0.1 to 10 μgS, the detection limit is 0.10μg S (equivalent to 20ng Sm⁻³ when ~ 1800m³ of air are filtered), and the relative standard deviations (n = 10) are 48 and 5.1% at the 0.10 and 4.0 μgS levels. Recoveries for 20 organic and inorganic compounds, including refractory sulfates, elemental sulfur, sulfides, sulfites, sulfonates and sulfones, vary from 79 to 88%. No interferences are observed for a number of non-sulfur-containing compounds, including nitrates, benzene, acetone, glucose, cellulose, silicates and carbonates. The technique was also used to determine the presence of non-sulfates and of non-water-soluble sulfates. Both TPS, using this technique, and water-soluble sulfate (WSS), using the methyl thymol blue method, were determined in daily air particulate samples collected at Whiteface Mountain, NY during both winter and summer. Comparision of TPS and WSS values showed that WSS could usually account for all of the sulfur present in the samples. The TPS concentrations ranged from 0.1 to 9.7μg Sm⁻³ and the contribution from acid-soluble sulfites and sulfides, elemental sulfur and volatile, S-containing organic compounds was negligible ( < 0.05 μgS m⁻³).     

Semivolatile behavior of dicarboxylic acids and other polar organic species at a rural background site (Nylsvley,RSA)

In this study aerosol samples from the South African savanna were analyzed for their polar organic constituents. Samples were collected with a front/back-up filter tandem system of quartz fiber filters (dual filter strategy). In all samples (n=15) dicarboxylic acids and a variety of phthalates, aldehydes and monocarboxylic acids were observed. Oxalic acid was the dominating compound with an average amount of 79.2 ng m⁻³ on the front filter and 11.3 ng m⁻³ on the back-up filter. The presence of significant concentrations of dicarboxylic acids on the back-up filter was rather unexpected. There are two possible sources to explain the presence of individual compounds on the back-up filter – particle penetration through the front filter or adsorption of compound parts from the gas phase. Interpretation of the data indicates that the dicarboxylic acid concentrations on the back-up filters appear to be caused by the adsorption of gaseous organic species. Dicarboxylic acids semivolatilic behavior is evident with this results. This conclusion refutes the commonly held view that dicarboxylic acids in the atmosphere were associated with the aerosol phase only. Additionally, it was found that the distribution of dicarboxylic acids between the gas and particle phase in the atmosphere is not only dependent on their vapor pressures. The actual gas phase concentration appears to be more determined by the chemical properties of the particles than by pure physical influences. Surprisingly, malonic acid exhibits an anomaly, as it does not show a semivolatile tendency.