Removal of hazardous metals from MSW fly ash—An evaluation of ash leaching methods

Incineration is a commonly applied management method for municipal solid waste (MSW). However, significant amounts of potentially hazardous metal species are present in the resulting ash, and these may be leached into the environment. A common idea for cleaning the ash is to use enhanced leaching with strong mineral acids. However, due to the alkalinity of the ash, large amounts of acid are needed and this is a drawback. Therefore, this work was undertaken in order to investigate some alternative leaching media (EDTA, ammonium nitrate, ammonium chloride and a number of organic acids) and to compare them with the usual mineral acids and water.All leaching methods gave a significant increase in ash specific surface area due to removal of soluble bulk (matrix) compounds, such as CaCO₃ and alkali metal chlorides. The use of mineral acids and EDTA mobilised many elements, especially Cu, Zn and Pb, whereas the organic acids generally were not very effective as leaching agents for metals. Leaching using NH₄NO₃ was especially effective for the release of Cu. The results show that washing of MSW filter ash with alternative leaching agents is a possible way to remove hazardous metals from MSW fly ash.     

An investigation on hazardous and odorous pollutant emission during cooking activities

In this study, the emission characteristics of various pollutants (e.g., reduced sulfur compounds (RSCs), aldehydes, volatile organic compounds (VOCs), and organic acids) were investigated in relation to 3 food types (including cabbage, clam, and coffee seeds) and 2 cooking methods (between mild and harsh treatments). The results indicated the strongest emissions from the roasted coffee seeds out of all 6 sample types. Among the pollutant types, the maximum emissions generally came from RSCs followed by aldehydes and acids. Among VOCs, toluene and methyl ethyl ketone were emitted most prominently. As most of these pollutants also represent key odorants, their concentrations are compared through a conversion into odor intensity (OI); the results showed the RSC group as the key odorants along with aldehydes and organic acid compounds. If the sum of odor intensity (SOI) is derived for each sample, they were in the descending order: roasting coffee seeds (6.50), frying cabbage (4.52), brewing coffee (4.14), grilling clam (3.91), boiling clam (3.89), and steaming cabbage (3.21). Their concentration data were also evaluated against regulation guidelines for indoor air quality (IAQ). Comparison of these pollutant data confirms that some cooking approaches can contribute significantly to the build up of nuisance and hazardous pollution concurrently.     

Analysis of a GC/MS thermal desorption system with simultaneous sniffing for determination of off-odor compounds and VOCs in fumes formed during extrusion coating of low-density polyethylene

A thermal desorption equipment introducing volatile organic compounds (VOCs) into the gas chromatographic/ mass spectrometric system (GC/MS) with simultaneous sniffing (SNIFF) is a suitable method for identifying the volatile organic off-odor compounds formed during the extrusion coating process of low-density polyethylene. Fumes emitted during the extrusion coating process of three different plastic materials were collected at two different temperatures (285 and 315 degrees C) from an outgoing pipe and near an extruder. The VOCs of fumes were analyzed by drawing a known volume of air through the adsorbent tube filled with a solid adsorbent (Tenax GR). The air samples were analyzed by using a special thermal desorption device and GC/MS determination. The simultaneous sniffing was carried out to detect off-odors and to assist in the identification of those compounds that contribute to tainting and smelling. The amounts of off-odor carbonyl compounds and the total content of the volatile organic compounds were determined. The most odorous compounds were identified as carboxylic acids while the majority of the volatile compounds were hydrocarbons. The detection and quantification of carboxylic acids were based on the characteristic ions of their mass spectra. The higher the extrusion temperature the more odors were detected. An important observation was that the total concentration of volatiles was dependent not only on the extrusion temperature but also on the plastic material.     

Production of biogas from municipal solid waste with domestic sewage

In this study, experiments were conducted to investigate the production of biogas from municipal solid waste (MSW) and domestic sewage by using anaerobic digestion process. The batch type of reactor was operated at room temperature varying from 26 to 36 degrees C with a fixed hydraulic retention time (HRT) of 25 days. The digester was operated at different organic feeding rates of 0.5, 1.0, 2.3, 2.9, 3.5 and 4.3kg of volatile solids (VS)/m(3) of digester slurry per day. Biogas generation was enhanced by the addition of domestic sewage to MSW. The maximum biogas production of 0.36m(3)/kg of VS added per day occurred at the optimum organic feeding rate of 2.9kg of VS/m(3)/day. The maximum reduction of total solids (TS) (87.6%), VS (88.1%) and chemical oxygen demand (COD) (89.3%) occurred at the optimum organic loading rate of 2.9kg of VS/m(3)/day. The quality of biogas produced during anaerobic digestion process was 68-72%.     

Subcritical water extraction for the remediation of phthalate ester-contaminated soil

Subcritical water has been used as an environment-friendly extraction fluid for many classes of organic compounds. It was used for the removal of phthalate esters (PEs), such as di-methyl phthalate, DMP; di-ethyl phthalate, DEP; di-iso-propyl phthalate, DIPP; di-n-butyl phthalate, DBP; benzyl butyl phthalate, BBP; di-n-pentyl phthalate, DpentP; di-n-hexyl phthalate, DHXP; di-heptyl phthalate, DheptP; di-2-ethylhexyl phthalate, DEHP; di-n-nonyl phthalate, DNP; di-n-octyl phthalate, DOP; di-n-decyl phthalate, DDP, in soil samples under the optimum condition of 250 °C and 10 MPa in our study. The soil samples cleaned with subcritical water were extracted by homemade accelerated solvent extraction system (ASE) and analyzed by HPLC-UV to check for soil remediation efficiency. Three types of soil collected at different sites in Taiwan have been tested. Although at higher PEs concentration levels, the modification of treatments may be necessary for satisfactory removal of the contaminants, soil samples of different PEs levels treated with subcritical water extraction (SCWE) were analyzed and the results indicated removal efficiency ranges of 80-90% for PEs spiked in soil samples. Soil samples contaminated with native DEHP were treated and gave comparable recovery efficiencies. Our results indicate that the applications of subcritical water as soil remediation for removal of PEs contaminant are feasible.     

Impact of low molecular weight organic acids and dissolved organic matter on sorption and mobility of isoproturon in two soils

Isoproturon is a selective herbicide belonging to the phenylurea family and widely used for pre- and post-emergence control of annual weeds. Soil amendments (e.g. organic compounds or dissolved organic matter) may affect environmental behavior and bioavailability of pesticides. However, whether the physiochemical process of isoproturon in soils is affected by organic amendments and how it is affected in different soil types are unknown. To evaluate the impact of low molecular weight organic acids (LMWOA) and dissolved organic matter (DOM) on sorption/desorption and mobility of isoproturon in soils, comprehensive analyses were performed using two distinct soil types (Eutric gleysols and Hap udic cambisols). Our analysis revealed that adsorption of isoproturon in Eutric gleysols was depressed, and desorption and mobility of isoproturon were promoted in the presence of DOM and LMWOA. However, the opposite result was observed with Hap udic cambisols, suggesting that the soil type affected predominantly the physiochemical process. We also characterized differential components of the soils using three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy and Fourier transform infrared (FT-IR) spectroscopy and show that the two soils displayed different intensity of absorption bands for several functional groups.     

New York hazardous substances emergency events surveillance: learning from hazardous substances releases to improve safety

Since 1993, the New York State Department of Health, funded by the Agency for Toxic Substances and Disease Registry, has collected data about non-petroleum hazardous substances releases through the Hazardous Substances Emergency Events Surveillance (NYHSEES) project. This study investigates risk factors for hazardous substances releases that may result in public health consequences such as injury or reported health effects. The 6428 qualifying events that occurred during the 10-year-period of 1993-2002 involved 8838 hazardous substances, 842 evacuations, more than 75,419 people evacuated, and more than 3120 people decontaminated. These events occurred both at fixed facilities (79%) and during transport (21%). The causative factors most frequently contributing to reported events were equipment failure (39%) and human error (33%). Five of the 10 chemicals most frequently associated with injuries were also among the 10 chemicals most frequently involved in reported events: sulfuric acid, hydrochloric acid, ammonia, sodium hypochlorite, and carbon monoxide. The chemical categories most frequently associated with events, and with events with adverse health effects were volatile organic compounds (VOCs) and solvents, and acids. Events with releases of hazardous substances were associated with injuries to 3089 people including employees (37%), responders (12%), the general public (29%) and students (22%). The most frequently reported adverse health effects were respiratory irritation, headache, and nausea or vomiting. Most of the injured were transported to the hospital, treated, and released (55%) or treated at the scene (29%). These data have been used for emergency response training, planning, and prevention activities to reduce morbidity and mortality from future events.     

Hydrophilic interaction liquid chromatography coupled to electrospray mass spectrometry of small polar compounds in food analysis

Reversed-phase liquid chromatography (RPLC) is commonly used to analyze nonvolatile components in food. However, polar low-molecular-weight compounds such as hydrophilic amino acids, di- and tripeptides, and organic acids are often not sufficiently retained and represent a challenge for RPLC. Hydrophilic interaction liquid chromatography in combination with electrospray mass spectrometry (HILIC-ESI-MS) on a carbamoyl-derivatized stationary phase was successfully employed to separate free amino acids and small polar peptides in complex food matrixes such as wheat gluten hydrolysate and Parmesan cheese. Glutamyl dipeptides were separated in a sequence-specific order with peptides with N-terminal glutamic acid residues eluting prior to their reverse sequence analogues. ESI-MSn detection in the positive ionization mode provided the necessary information to unambiguously identify isobaric peptides due to their characteristic fragmentation patterns. The technique also proved useful to separate and identify glycoconjugates between amino acids and reducing sugars (Amadori compounds). The investigation of organic acids present in food used a mobile phase comprising ammonium acetate buffer at pH 7 and mass spectrometric detection in the negative ionization mode.     

Thermal hazard assessment of nitrobenzene/dinitrobenzene mixtures

The aims of this study were to improve the emission test method for the 20 L small chamber standardized in Korea using paints and to develop an optical test method for paints. The emission factors of the total volatile organic compounds (TVOC) and formaldehyde from oil-based paints, emulsion paints and water-dispersion paints coated at 300 g/m(2) and cured for 24 (48)h were determined using the 20 L small chamber method. The emission factors of TVOC and formaldehyde from all paints under steady state conditions were determined after 7 days with 24 (48)h of curing. The Korean standards require that paints be measured and analyzed on the third day after a test. However, the emission factors of TVOC and formaldehyde from the paints only began to stabilize 7 days after installing the samples. Until now, the emission test results have been reported mainly as concentration vs. time or emission factor vs. time profiles of TVOC and formaldehyde. The emission factors of the target volatile organic compounds (VOCs) and aldehyde types were obtained under specific test conditions according to the different coating weights. For all target volatile organic compounds and aldehyde types examined, the paint coating weight had an effect on emission.     

Analysis of adsorption equilibrium of volatile chlorinated organic compounds to dry soil

Adsorption is one of the main mechanisms of soil contamination by hazardous volatile chlorinated organic compounds. The adsorption equilibriums of six volatile organic chlorinated compounds to three dry soils were investigated using batch adsorption experiments. The adsorption equilibriums for the dry soils could be expressed by the Dubinin-Astakhov equation. The equation's parameters were analyzed with the characteristic values of the soils and compounds. No correlation between the values of the affinity coefficients, beta, and the molecular volume, Mv, was found. W(0) could be expressed by the functions of a pore volume of less than 10 nm, V(<10 nm), or the specific surface area, S. The adsorbed amount could be estimated using equations relating E(0), V(<10 nm) (or S), and beta. The predicted amounts agreed well with the measured data.     

Effects of dissolved low molecular weight organic acids on oxidation of ferrous iron by Acidithiobacillus ferrooxidans

A few researchers have reported on work concerning bioleaching of heavy-metal-contaminated soil using Acidithiobacillus ferrooxidans, since this acidophile is sensitive to dissolved low molecular weight (LMW) organic acids. Iron oxidation by A. ferrooxidans R2 as well as growth on ferrous iron was inhibited by a variety of dissolved LMW organic acids. Growth experiments with ferrous iron as an oxidant showed that the inhibition capability sequence was formic acid>acetic acid>propionic acid>oxalic acid>malic acid>citric acid. The concentrations that R2 might tolerate were formic acid 0.1mmolL(-1) (2mmolkg(-1)soil), acetic and propionic acids 0.4mmolL(-1) (8mmolkg(-1)soil), oxalic acid 2.0mmolL(-1) (40mmolkg(-1)soil), malic acid 20mmolL(-1) (400mmolkg(-1)soil), citric acid 40mmolL(-1) (800mmolkg(-1)soil), respectively. Although R2 was sensitive to organic acids, the concentrations of LMW organic acids in the contaminated soils were rather lower than the tolerable levels. Hence, it is feasible that R2 might be used for bioleaching of soils contaminated with metals or metals coupled with organic compounds because of the higher concentrations of LMW organic acids to which R2 is tolerant.     

Optimization of municipal solid waste leaching test procedure: assessment of the part of hydrosoluble organic compounds

Despite national recycling campaigns, the amount of municipal solid waste (MSW) to be treated remains very important in France with almost 39% of the waste produced going to landfills. Therefore with the increasing concern over sustainable development and energy valorization, it seems essential to optimize current treatment methods and develop new preparation techniques of the waste. Nevertheless an important first step to take into account is to evaluate the waste using a different method than biogas production. In this perspective, the leaching test (LT) could be used as a tool to evaluate the ability of a waste to mobilize organic and mineral compounds. This research aims at optimizing a leaching test protocol mainly adapted to organic waste in order to be used on MSW to assess the fractions of both fast and slow mobilized organic matter. Several leaching tests have thus been implemented, optimized and compared in terms of accessible organic matter in the waste. Results have shown that the test conditions have a great influence on the mobilization of pollutants. The duration of the test affects mainly the quantity and quality of organic molecules extracted. The renewal of the eluent does not properly simulate the conditions of a landfill. The results would be used to assess the performance and the efficiency of new ways of waste pretreatment.     

The behaviour of Al in MSW incinerator fly ash during thermal treatment

Fly ash from municipal solid waste (MSW) incinerators contains leachable metals, including potentially hazardous heavy metals. The metal content of the fly ash can be reduced by thermal treatment, which vaporizes the volatile metal compounds. After heat treatment of fly ash at 1000 degrees C for 3 h, less metal was able to be leached from the thermally treated ash than from the ash without thermal treatment. Al and Cr were the exceptions. These metals were more soluble in the ash that had been thermally treated. This paper focuses on the leaching behaviour of Al only. Both simple and sequential extraction leaching tests showed that the leachable Al for the heat-treated fly ash is about twice that of the untreated fly ash. The sequential test further revealed that (i) the majority of the leachable Al is associated with Fe-Mn oxides in the fly ash, and (ii) most of the unleachable Al resides in the silicate matrices of the heat-treated and untreated fly ash. Pure chemicals, Al(2)O(3), CaO and CaCl(2), simulating the relevant ingredients in the fly ash, were used for studying their reactions at 1000 degrees C. The aluminum compounds were identified by X-ray Diffraction (XRD). Two new chemical phases produced by the thermal treatment were identified; Ca(AlO(2))(2) and 12CaO.7Al(2)O(3). Their formation suggests a mechanism whereby thermal treatment of fly ash would produce more soluble Al.     

A foundation for the risk-based treatment of gasoline-contaminated soils using modified Fenton's reactions

The relative oxidation of representative aromatic and aliphatic hydrocarbons found in gasoline was evaluated to provide the foundation for risk-based treatment of petroleum-contaminated soils and groundwater using modified Fenton's reagent (catalyzed hydrogen peroxide). Aromatic components of gasoline are considered more hazardous than the aliphatic fractions due to their higher mobility in the subsurface and their higher acute and chronic toxicities. Benzene, toluene, and mixed xylenes (BTX) were selected as aromatic compounds representative of unleaded gasoline, while nonane, decane, and dodecane (NDD) were used as model aliphatic compounds. The effects of hydrogen peroxide (H(2)O(2)) concentration, iron catalyst concentration, and pH on the degree of treatment of the model compounds were investigated using central composite rotatable experimental designs. Oxidation of the aromatic compounds required less iron and less H(2)O(2) than did oxidation of the aliphatic compounds, while proceeding more effectively at near-neutral pH. Greater than 95% of the BTX was treated at near-neutral pH using 2. 5% H(2)O(2) and 12.5 mM iron (III), while only 37% nonane, 7% decane, and 1% dodecane oxidation was achieved under the same conditions. The results show that the more toxic and mobile aromatic fraction was more effectively oxidized using less H(2)O(2) and more economical conditions, including near-neutral pH, compared to the aliphatic fraction. A process design based on treating only the aromatic fraction of petroleum may provide significantly lower costs when using modified Fenton's reagent for the treatment of contaminated soils and groundwater.     

纸质包装材料中挥发性有机物迁移量的测定

目的研究纸质包装材料中挥发性有机物向食品模拟物中的迁移量。方法选取改性聚苯醚作为食品模拟物,首次建立模拟物MPPO直接顶空进样-气相色谱/质谱联用法测定包装用纸中23种有机挥发物质迁移量的方法。结果该法测定23种挥发性物质的相关系数R均大于0.998,相对标准偏差为1.4%~4.6%(n=7),检出限为0.03~0.60 mg/m2,加标回收率为81.2%~110.2%。结论该法无需前处理,简单快速,灵敏度高,重现性好,能满足包装用纸中23种有机挥发性物质迁移量的测定要求。     

Thermodynamic Analysis of the Gasification of Municipal Solid Waste

This work aims to understand the gasification performance of municipal solid waste (MSW) by means of thermodynamic analysis. Thermodynamic analysis is based on the assumption that the gasification reactions take place at the thermodynamic equilibrium condition, without regard to the reactor and process characteristics. First, model components of MSW including food, green wastes, paper, textiles, rubber, chlorine-free plastic, and polyvinyl chloride were chosen as the feedstock of a steam gasification process, with the steam temperature ranging from 973 K to 2273 K and the steam-to-MSW ratio (STMR) ranging from 1 to 5. It was found that the effect of the STMR on the gasification performance was almost the same as that of the steam temperature. All the differences among the seven types of MSW were caused by the variation of their compositions. Next, the gasification of actual MSW was analyzed using this thermodynamic equilibrium model. It was possible to count the inorganic components of actual MSW as silicon dioxide or aluminum oxide for the purpose of simplification, due to the fact that the inorganic components mainly affected the reactor temperature. A detailed comparison was made of the composition of the gaseous products obtained using steam, hydrogen, and air gasifying agents to provide basic knowledge regarding the appropriate choice of gasifying agent in MSW treatment upon demand.     

Identification of weak and strong organic acids in atmospheric aerosols by capillary electrophoresis/mass spectrometry and ultra-high-resolution fourier transform ion cyclotron resonance mass spectrometry

A novel approach using a combination of capillary electrophoresis/mass spectrometry (CE/MS) and off-line Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) revealed the structural details of acidic constituents of atmospheric organic aerosol. Both techniques utilized electrospray ionization (ESI), a soft ionization method, to facilitate the analysis of complex mixtures of organic compounds. CE/ESI-MS using an UltraTrol LN-precoated capillary and acidic background electrolytes at different pH values (2.5 and 4.7) was used to differentiate between weak (carboxylic) and strong (sulfonic) organic acids. On the basis of the electrophoretic mobility, m/z constraints from CE/ESI(-)-MS, and elemental composition information retrieved from off-line FTICR-MS, a variety of aliphatic and aromatic carboxylic acids (CHO-bearing molecules), nitrogen-containing carboxylic acids (CHON-bearing molecules), organosulfates (CHOS-bearing molecules), and (nitrooxy)organosulfates (CHONS-bearing molecules) were tentatively identified in the Oasis-HLB-extracted urban PM(2.5) (particulate matter with an aerodynamic diameter of <2.5 μm). The chemical known/unknown structures of detected compounds were confirmed by the semiempirical Offord model (effective mobility linearly correlated to Z/M(2/3)). The majorities of the identified compounds are products of atmospheric reactions and are known contributors to secondary organic aerosols.     

Metabolite profiling of human amniotic fluid by hyphenated nuclear magnetic resonance spectroscopy

The metabolic profiling of human amniotic fluid (HAF) is of potential interest for the diagnosis of disorders in the mother or the fetus. In order to build a comprehensive metabolite database for HAF, hyphenated NMR has been used, for the first time, for systematic HAF profiling. Experiments were carried out using reverse-phase (RP) and ion-exchange liquid chromatography (LC), in order to detect less and more polar compounds, respectively. RP-LC conditions achieved good separation of amino acids, some sugars, and xanthines. Subsequent NMR and MS analysis enabled the rapid identification of 30 compounds, including 3-methyl-2-oxovalerate and 4-aminohippurate identified in HAF for the first time, to our knowledge. Under ion-exchange LC conditions, a different set of 30 compounds was detected, including sugars, organic acids, several derivatives of organic acids, and amino acids. In this experiment, five compounds were identified for the first time in HAF: D-xylitol, amino acid derivatives (N-acetylalanine, N-acetylglycine, 2-oxoleucine), and isovalerate. The nonendogenous nature of some metabolites (caffeine, paraxanthine, D-xylitol, sorbitol) is discussed. Hyphenated NMR has allowed the rapid detection of approximately 60 metabolites in HAF, some of which are not detectable by standard NMR due to low abundance (microM) and signal overlap thus enabling an extended metabolite database to be built for HAF.     

Optimization of the solidification/stabilization process of MSW fly ash in cementitious matrices

The solidification/stabilization (S/S) process of municipal solid waste (MSW) fly ash in cementitious matrices was investigated in order to ascertain the feasibility of a washing pretreatment of fly ash with water as a means of maximizing the ash content of cementitious mixtures. Four types of fly ash resulting from different Italian MSW incineration plants and ASTM Type III Portland cement were used in this study. Ash-cement mixtures with different fly ash/cement (FA/C) ratios were made using untreated and washed fly ash. Washing of fly ash with water was realized by a two-stage treatment (liquid/solid=25; mixing time=15 min for each stage). The cementitious mixtures were characterized for water demand, setting time, mechanical strength, and heavy metals leachability. Comparison between the above properties of mixtures incorporating untreated and washed fly ash (particularly, setting characteristics), coupled with economical evaluation of the S/S process when applied to untreated and washed fly ash, proved the feasibility of washing pretreatment as a means of maximizing the incorporation of MSW fly ash in cementitious matrices (ash content up to 75%-90% by weight of total solid).