Comparative study of methodologies for the analysis of PCDDs and PDCFs in powdered full-fat milk. PCB, PCDD and PCDF levels in commercial samples from Spain

Feasibility of two different extraction methods involving solid-liquid extraction and Soxhlet extraction, previously used for the determination of lipid contents and PCB levels on powdered full-fat milk, are now examined for simultaneous PCDD/F analysis. The results of this study are consistent with those found for PCBs. The solid-liquid procedure provides the most efficient extraction of both labelled spiked and endogenous PCDD/Fs with the lowest variability. The average recoveries were 101% (R.S.D. = 6.9%) for 13C12-2,3,7,8-TCDD and 95% (R.S.D. = 11%) for 13C12-1,2,3,4,7,8-HxCDD. The R.S.D.s for endogenous 2,3,7,8-PCDD/Fs were in the 9.3-25% range. In addition, this methodology simplified the subsequent clean-up step as it allowed a semi-selective extraction of the apolar lipids from the milk. The proposed method was applied to simultaneous PCB and PCDD/F analyses in different brands of powdered full-fat milks commercially available in Spain. In all cases, very similar PCB and PCDD/F levels were found. Differences among batches from the same manufacturer were even lower. The total i-TEQ average for PCDDs and PCDFs in the 22 powdered full-fat milk samples analysed was 1.87 pg/g fat basis. This value was similar to those found in cow's milk from other European countries.     

Comparison of two reference black carbons using a planar PCB as a model sorbate

In studies assessing sorption of hydrophobic organic compounds (HOCs) in natural systems, the choice of an appropriate reference black carbon, which can represent environmental black carbon (BC), is essential. This study compared isotherms of two commonly available and distinct reference BCs (n-hexane soot (BCRM) and diesel particulate matter (SRM 2975)) and a natural sediment from a source with little black carbon (Lake Hartwell, SC) using 3,3',4-trichlorobiphenyl (IUPAC #35) as a model sorbate. There was greater sorptivity for PCB-35 by BCRM than by SRM 2975. The observed differences in sorption between the two reference black carbons for PCB-35 may be ascribed to the different chemical characteristics of the black carbons. Differences in pore volume distribution at <16A pore width are less likely to be responsible for the observed differences in sorption. The elemental analysis confirmed that BCRM was a pure n-hexane soot because only C, H and O were measured. In contrast, SRM 2975 also contained N and S and a higher O% than BCRM. Compared to the low BC sediment, the two reference BCs had greater pore volume distributions, surface areas, total pore volumes and sorption. The observed nF (i.e., Freundlich exponent) values for PCB indicated greater linearity of the isotherms for the natural sediment than for the reference black carbons. For designing studies of sorption of HOCs in natural systems, in particular, when PCBs are contaminants of concern, results of this study can aid selection of the appropriate reference BCs.     

Preparation of sulfurized powdered activated carbon from waste tires using an innovative compositive impregnation process

The objective of this study is to develop an innovative compositive impregnation process for preparing sulfurized powdered activated carbon (PAC) from waste tires. An experimental apparatus, including a pyrolysis and activation system and a sulfur (S) impregnation system, was designed and applied to produce sulfurized PAC with a high specific surface area. Experimental tests involved the pyrolysis, activation, and sulfurization of waste tires. Waste-tire-derived PAC (WPAC) was initially produced in the pyrolysis and activation system. Experimental results indicated that the Brunauer-Emmett-Teller (BET) surface area of WPAC increased, and the average pore radius of WPAC decreased, as water feed rate and activation time increased. In this study, a conventional direct impregnation process was used to prepare the sulfurized PAC by impregnating WPAC with sodium sulfide (Na2S) solution. Furthermore, an innovative compositive impregnation process was developed and then compared with the conventional direct impregnation process. Experimental results showed that the compositive impregnation process produced the sulfurized WPAC with high BET surface area and a high S content. A maximum BET surface area of 886 m2/g and the S content of 2.61% by mass were obtained at 900 degrees C and at the S feed ratio of 2160 mg Na2S/g C. However, the direct impregnation process led to a BET surface area of sulfurized WPAC that decreased significantly as the S content increased.     

Occurrence of polychlorinated biphenyls (PCBs) together with sediment properties in the surface sediments of the Bering Sea, Chukchi Sea and Canada Basin

The spatial distribution and potential source of polychlorinated biphenyls (PCBs) in surface sediments from Bering Sea, Chukchi Sea, and Canada Basin and the relationship between PCBs and sedimentary properties including grain size, water content, loss on ignition, total organic carbon, and black carbon were explored. ΣPCBs (the sum of the detected PCB congeners) concentrations fluctuated in the study area, ranging from 22-150, 60-640 and 24-600 pg g(-1) dry weight for the Bering Sea, Chukchi Sea, and Canada Basin. A similar homologue pattern was observed at different locations, with tri-chlorinated PCBs being the dominant homologue, implying that the PCBs came mainly from the atmospheric transportation and deposition and ocean current transportation. No apparent co-relationships between PCB concentrations and sediment properties were obtained, indicating that the distribution of PCBs was not only controlled by their source, but also by the multi-factors such as atmospheric transport and depositing, mixing, partitioning and sorption in the water column and sediments.     

Preparation of Sulfurized Powdered Activated Carbon from Waste Tires Using an Innovative Compositive Impregnation Process

Abstract

The objective of this study is to develop an innovative compositive impregnation process for preparing sulfurized powdered activated carbon (PAC) from waste tires. An experimental apparatus, including a pyrolysis and activation system and a sulfur (S) impregnation system, was designed and applied to produce sulfurized PAC with a high specific surface area. Experimental tests involved the pyrolysis, activation, and sulfurization of waste tires. Waste-tire-derived PAC (WPAC) was initially produced in the pyrolysis and activation system. Experimental results indicated that the Brunauer-Emmett-Teller (BET) surface area of WPAC increased, and the average pore radius of WPAC decreased, as water feed rate and activation time increased. In this study, a conventional direct impregnation process was used to prepare the sulfurized PAC by impregnating WPAC with sodium sulfide (Na₂S) solution. Furthermore, an innovative compositive impregnation process was developed and then compared with the conventional direct impregnation process. Experimental results showed that the compositive impregnation process produced the sulfurized WPAC with high BET surface area and a high S content. A maximum BET surface area of 886 m²/g and the S content of 2.61% by mass were obtained at 900°C and at the S feed ratio of 2160 mg Na₂S/g C. However, the direct impregnation process led to a BET surface area of sulfurized WPAC that decreased significantly as the S content increased.     

Preparation and characterisation of activated carbon from waste tea by physical activation using steam

ABSTRACT

In this study, the feasibility of preparing activated carbon from waste tea by physical activation using steam was investigated. The effects of activation temperature on yield and pore properties of the prepared activated carbon were studied. The yield decreased with increased activation temperature owing to the decomposition of cellulose and hemicellulose. The specific surface area and pore volume of the activated carbon were estimated using the Brunauer–Emmett–Teller method, Langmuir equation, and t-plot method. The specific surface area and micropore volume increased with increases in activation temperature, as additional volatile materials were released. The specific surface area significantly decreased at first but slightly increased with increasing activation time. The maximum specific surface area reached 995 m²/g at an activation temperature of 800 °C with a water flow rate of 0.075 g/min and a constant hold time of 0.5 hr. According to the nitrogen adsorption isotherms, micropores mainly developed when the activation temperature was below 800 °C, and both micropores and mesopores developed when it was above 800 °C. The results showed that activation temperature significantly affected micropore and mesopore volumes, as well as the specific surface area of the activated carbon. Overall, waste tea was found to be an attractive raw material for producing low-cost activated carbon.

Implications: Every year, a large amount of waste tea is generated after extraction. The high carbon content of waste tea showed that it can be used as raw material to produce activated carbon. This study investigated the feasibility of preparing activated carbon from waste tea by physical activation using steam. Temperature and time were found to have clear effects on pore properties. Our proposed method and raw material are more environmentally friendly and involve low cost. Furthermore, this offers a potential solution to the problems of waste tea disposal and low-cost activated carbon production.     

Determination of the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon using thermogravimetric analysis

This study investigated the use of thermogravimetric analysis (TGA) to determine the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon (PAC). The technique is commonly applied to remove mercury-containing air pollutants from gas streams emitted from municipal solid waste incinerators. An alternative form of powdered activated carbon derived from a pyrolyzed tire char was prepared for use herein. The capacity of waste tire-derived PAC to adsorb vapor-phase HgCl2 was successfully measured using a self-designed TGA adsorption system. Experimental results showed that the maximum adsorptive capacities of HgCl2 were 1.75, 0.688, and 0.230 mg of HgCl2 per gram of powdered activated carbon derived from carbon black at 30, 70, and 150 degrees C for 500 microg/m3 of HgCl2, respectively. Four adsorption isotherms obtained using the Langmuir, Freundlich, Redlich-Peterson, and Brunauer-Emmett-Teller (BET) models were used to simulate the adsorption of HgCl2. The comparison of experimental data associated with the four adsorption isotherms indicated that BET fit the experimental results better than did the other isotherms at 30 degrees C, whereas the Freundlich isotherm fit the experimental results better at 70 and 150 degrees C. Furthermore, the calculations of the parameters associated with Langmuir and Freundlich isotherms revealed that the adsorption of HgCl2 by PAC-derived carbon black favored adsorption at various HgCl2, concentrations and temperatures.     

Dechlorination of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans on fly ash

Dechlorination of commercial mixtures of polychlorinated biphenyls (PCB) as well as polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) on extracted and non-extracted fly ash obtained from municipal waste incinerator (MWI) was studied in closed systems under nitrogen atmosphere at temperatures of 260°C and 340°C. Decomposition results (given as the difference between PCB or PCDD/F molar amounts before and after the experiment (in %) due predominantly to dechlorination reactions) and detoxification data (expressed similarly but related to toxic PCB and PCDD/F congeners only and given in I-TEQ units) are reported. Detoxification of Delor 105/80T at 260°C and 340°C at a loading of 0.65 wt% was 99.48% and 100%, respectively. The decomposition of Delor 103 at 340°C and for the loading of 0.75 wt% corresponded to 99.99%. The detoxification capability of PCDD/Fs on extracted and non-extracted fly ash for loading of 130 and 264 ng/0.4 g of fly ash at 340°C made 96 and 98%, respectively.     

Preparation of activated carbons from raw and biotreated agricultural residues for removal of volatile organic compounds

Activated carbons with diverse physical and chemical properties were produced from four agriculture residues, including raw barley husk, biotreated barley husk, rice husk, and pistachio shell. Results showed that with adequate steam activation (30-90 min, 50% H2O(g),/50% N2), activated carbons with surface areas between 360 and 950 m2 g(-1) were developed. Further increases in the activation time destroyed the pore structure of activated carbons, which resulted in a decrease in the surface area and pore volume. Biotreated agricultural residues were found to be suitable precursors for producing mesoporous activated carbons. The oxygen content of activated carbons increased with increasing activation time. Results from X-ray photoelectron spectroscopy examination further suggested that H2O molecules react with the carbon surface, enhancing the deconvoluted peak area of carbonyl and carboxyl groups. Equilibrium adsorption of toluene indicated that the adsorption capacities increased with an increase in the inlet toluene concentration and a decrease in temperature. The adsorption isotherms were successfully fitted with Freundlich, Langmuir, and Dubinin-Radushkevich equations. Activated carbons derived from agricultural residues appear to be more applicable to adsorb volatile organic compounds at a low concentration and high-temperature environment.     

Effects of sample preparation on the measurement of organic carbon,hydrogen, nitrogen,sulfur, and oxygen concentrations in marine sediments

The elemental composition of marine sediment provides useful information for the study of environmental processes including biogeochemical cycling and contaminant partitioning. It is common practice to acidify marine sediment samples to remove carbonate before measuring the concentrations of organic carbon (C). To date, however the effects of acidification on the concentrations of hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) in marine sediments have not been explicitly addressed. Acidification may contaminate or alter the sediment samples and create experimental artifacts affecting the validity of resulting H/C, C/N and O/C ratios. The objective of this study was to quantify how various preparation techniques affect the measured concentrations of C, H, N, S and O in marine sediments. Effects of four different pretreatments: unacidified (whole), acidification by HCl vapor, acidification by direct addition of HCl, and combustion were evaluated using five marine sediments and a standard reference material. The magnitude of carbonate loss between the vapor and direct acidification treatments was evaluated using stable C isotope analysis. Carbonates were most effectively removed by direct addition of HCl; and our results agree with findings of other studies which found direct addition of HCl to be the most accurate method for measuring organic C. However, the acid treatments elevated the apparent concentration of H and O; and in a few cases concentrations of N and S were significantly affected by acidification. In general, combustion significantly reduced all elemental concentrations compared to the whole sample. Based on these results, we recommend analysis of the untreated whole sediment for determining N, H, O, and S.     

气相沿面放电—活性炭纤维吸附联合降解双酚A废水研究

利用气相沿面放电—活性炭纤维(ACF)吸附(简称放电—吸附)联合处理含双酚A(BPA)废水,探讨了联合处理对BPA的降解效果,并通过处理过程中O3利用率变化以及处理前后ACF的表观状态变化分析了反应的作用机制。结果表明,放电—吸附联合处理相比单独放电和单独ACF吸附能显著提高BPA的降解率;在一定范围内,加大放电电压能提高放电—吸附联合处理的BPA降解效果,但放电电压超过一定值后,放电产生的O3量进一步增多,对ACF表面的结构破坏作用增加,反而导致BPA的降解效果降低,本研究较佳的放电电压为8.5kV;扫描电镜分析结果表明,经放电—吸附联合处理后,ACF表面出现大量的孔道,提高了表面的BPA富集浓度,同时也增加反应的活性位点;傅里叶变换红外光谱分析结果表明,联合处理后ACF表面的C—O、C=C、O—H等官能团都有所减少,可能是联合处理过程中O3等活性物质与ACF表面的这些还原性官能团发生了反应,诱导O3分解出了更多的自由基,从而促进了BPA的降解。     

Determination of the Adsorption Isotherm of Vapor-Phase Mercury Chloride on Powdered Activated Carbon Using Thermogravimetric Analysis

Abstract

This study investigated the use of thermogravimetric analysis (TGA) to determine the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon (PAC). The technique is commonly applied to remove mercury-containing air pollutants from gas streams emitted from municipal solid waste incinerators. An alternative form of powdered activated carbon derived from a pyrolyzed tire char was prepared for use herein. The capacity of waste tire-derived PAC to adsorb vapor-phase HgCl₂ was successfully measured using a self-designed TGA adsorption system. Experimental results showed that the maximum adsorptive capacities of HgCl₂ were 1.75, 0.688, and 0.230 mg of HgCl₂ per gram of powdered activated carbon derived from carbon black at 30, 70, and 150 °C for 500 µg/m³ of HgCl₂, respectively. Four adsorption isotherms obtained using the Langmuir, Freundlich, Redlich-Peterson, and Brunauer–Emmett–Teller (BET) models were used to simulate the adsorption of HgCl₂. The comparison of experimental data associated with the four adsorption isotherms indicated that BET fit the experimental results better than did the other isotherms at 30 °C, whereas the Freundlich isotherm fit the experimental results better at 70 and 150 °C. Furthermore, the calculations of the parameters associated with Langmuir and Freundlich isotherms revealed that the adsorption of HgCl₂ by PAC-derived carbon black favored adsorption at various HgCl₂ concentrations and temperatures.     

废轮胎粉等离子体热解过程中硫的分布与转化初步研究

采用等离子体热解法处理废轮胎粉,分析硫在热解过程中的分布与转化。考察了等离子体输入功率、废轮胎粉进料速率、水蒸气以及白云石的加入对硫分布的影响。结果表明,等离子体热解过程中,硫在固体产物中的分布率为79.50%～97.50%,即大部分硫主要分布在固体产物中;气体产物中的硫主要为H2S,且H2S浓度随输入功率的增加、废轮胎粉进料速率的降低而降低,同时,在热解过程中加入外加物料(水蒸气、白云石)也将不同程度地降低气体产物中H2S浓度。废轮胎粉中的碳黑在热解后生成热解碳黑,采用核磁共振和X射线光电子能谱分析热解碳黑,结果显示,热解碳黑除表面性质发生了一些变化外,其主体化学性质与商业碳黑基本一致,硫在热解碳黑中以硫化物的形态存在。     

Deodorization of dimethyl sulfide using a discharge approach at room temperature

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

Production of activated carbons from pyrolysis of waste tires impregnated with potassium hydroxide

Activated carbons were produced from waste tires using a chemical activation method. The carbon production process consisted of potassium hydroxide (KOH) impregnation followed by pyrolysis in N2 at 600-900 degrees C for 0-2 hr. The activation method can produce carbons with a surface area (SA) and total pore volume as high as 470 m2/g and 0.57 cm3/g, respectively. The influence of different parameters during chemical activation, such as pyrolysis temperature, holding time, and KOH/tire ratio, on the carbon yield and the surface characteristics was explored, and the optimum preparation conditions were recommended. The pore volume of the resulting carbons generally increases with the extent of carbon gasified by KOH and its derivatives, whereas the SA increases with degree of gasification to reach a maximum value, and then decreases upon further gasification.     

Encapsulation of nonmetallic fractions recovered from printed circuit boards waste with thermoplastic

The present work includes a process for encapsulation by combining substantially simultaneously dry nonmetallic printed circuit boards (PCBs) powder and recycled high-density polyethylene (rHDPE) in an extruder to form a homogenous matrix. The extruded materials were then molded into standard tensile, flexural, and impact properties testing specimens. Nonmetallic PCB mainly consists of large amount of glass fiber–reinforced epoxy resin materials. Incorporation of 50 wt% nonmetallic PCB in rHDPE matrix had increased the flexural strength and modulus by 35% and 130%, respectively. Tensile strength reported to be constant without much improvement. However, the Young’s modulus has increased by 180%, with incorporation of 50 wt% nonmetallic PCB. The addition of 6 phr (parts per hundred) maleated polyethylene (MAPE) resulted in 2-fold increase in tensile and flexural strength. Regarding the leaching properties, Cu was identified as the metal that leached at the highest level from the raw nonmetallic PCB, at 59.09 mg/L. However, after the nonmetallic PCB was filled in rHDPE/PCB composites, the concentration of Cu was reduced far below the regulatory limit, to only 3 mg/L. Thermal properties of composites were studied, and it was found out that incorporation of nonmetallic PCB fillers in rHDPE resulted in low thermal conductivity, whereas mechanical strength of the composites showed maximum improvements at 220 °C. Overall, the encapsulation technique using nonmetallic PCB waste has formed a monolithic waste form that provides a barrier to the dispersion of wastes into the environment.

ImplicationsNonmetallic materials reclaimed from waste PCBs were used to analyze the chemical composition, and it was found that nonmetalllic PCBs mainly consist of glass fiber–reinforced epoxy resin materials. With such millions of glass fibers in nonmetallic PCBs, there are mass-excellent supporting bodies that enhance the mechanical properties of composites. In fact, utilization of nonmetallic PCB waste as filler in composites can dramatically restrain the solubility of heavy metals in leachate solution, thus making it safe to be used in practical products.     

Catalytic activity of Ru/Al2O3 for ozonation of dimethyl phthalate in aqueous solution

With dimethyl phthalate as the model pollutant and Ru/Al(2)O(3) as catalyst, this paper systemically investigates the removal of total organic carbon (TOC) of system. Our results have confirmed that Ru/Al(2)O(3) can significantly increase the effect of ozonation. TOC removal in 120 min can reach 72% while only 24% with ozone alone. The optimal catalyst preparing condition was 0.1 wt% Ru content, 600 degrees C calcination temperature, 0.5-1.0mm particle diameter, which is characterized by a high surface area and a large population of surface active sites. The contrasting experiments of ozone alone, catalyst adsorption after ozonation, and catalytic ozonation confirmed that catalytic reaction was the most important process to TOC removal in system with Ru/Al(2)O(3) as catalyst.     

厕所污水回用脱色方法及机理研究

采用投加粉末活性炭对经膜生物反应器处理的厕所回用水(膜出水)进行脱色.对厕所回用水中色度物质的成分及分子量分布,对选定高效适用的活性炭及活性炭对厕所回用水中色度物质的去除机理进行了探讨.试验结果表明,使膜出水显色的物质是一类在紫外区有明显吸收或有特征吸收峰的有机物,且大部分物质分子量分布在6～60 KD的范围内.在选定有高效脱色效果的活性炭时,要综合考虑活性炭的亚甲基蓝吸附值和焦糖脱色率2个指标,其中焦糖脱色率有着更重要的意义.厕所回用水脱色是对其各个分子量区间颜色物质去除效果的总和.     

Hydrogen production using thermocatalytic decomposition of methane on Ni<Subscript>30</Subscript>/activated carbon and Ni<Subscript>30</Subscript>/carbon black

Hydrogen is an energy carrier of the future need. It could be produced from different sources and used for power generation or as a transport fuel which mainly in association with fuel cells. The primary challenge for hydrogen production is reducing the cost of production technologies to make the resulting hydrogen cost competitive with conventional fuels. Thermocatalytic decomposition (TCD) of methane is one of the most advantageous processes, which will meet the future demand, hence an attractive route for CO_x free environment. The present study deals with the production of hydrogen with 30 wt% of Ni impregnated in commercially available activated carbon and carbon black catalysts (samples coded as Ni₃₀/AC and Ni₃₀/CB, respectively). These combined catalysts were not attempted by previous studies. Pure form of hydrogen is produced at 850 °C and volume hourly space velocity (VHSV) of 1.62 L/h g on the activity of both the catalysts. The analysis (X-ray diffraction (XRD)) of the catalysts reveals moderately crystalline peaks of Ni, which might be responsible for the increase in catalytic life along with formation of carbon fibers. The activity of carbon black is sustainable for a longer time compared to that of activated carbon which has been confirmed by life time studies (850 °C and 54 sccm of methane).     

Evaluation of the thermal/optical reflectance method for discrimination between char- and soot-EC

Many optical, thermal and chemical methods exist for the measurement of elemental carbon (EC) but are unable or neglect to differentiate between the different forms of EC such as char- or soot-EC. The thermal/optical reflectance (TOR) method applies different temperatures for measuring EC and organic carbon (OC) contents through programmed, progressive heating in a controlled atmosphere, making available eight separate carbon fractions - four OC, one pyrolyzed organic carbon, and three EC. These fractions were defined by temperature protocol, oxidation atmosphere, and laser-light reflectance/transmittance. Stepwise thermal evolutional oxidation of the TOR method makes it possible to distinguish char- from soot-EC. In this study, different EC reference materials, including char and soot, were used for testing it. The thermograms of EC reference materials showed that activation energy is lower for char- than soot-EC. Low-temperature EC1 (550 degrees C in a 98% He/2% O2 atmosphere) is more abundant for char samples. Diesel and n-hexane soot samples exhibit similar EC2 (700 degrees C in a 98% He/2% O2 atmosphere) peaks, while carbon black samples peaks at both EC2 and EC3 (800 degrees C in a 98% He/2% O2 atmosphere). These results supported the use of the TOR method to discriminate between char- and soot-EC.