Fluorescence excitation-emission matrix combined with regional integration analysis to characterize the composition and transformation of humic and fulvic acids from landfill at different stabilization stages

Fluorescence excitation-emission matrix spectroscopy (EEMs) combined with fluorescence regional integration (FRI) analysis was used to investigate the composition and transformation of humic acid (HA) and fulvic acid (FA) from landfill. The EEMs of HAs at different landfill ages were characterized by two typical fluorescence chromophores with Ex/Em pairs at Ex = 420-470 nm/Em = 490-530 nm and Ex = 345-375 nm/Em = 450-465 nm. EEMs of FA were featured by other two distinctly different fluorophores with Ex/Em pairs at Ex = 315-335 nm/Em = 420-440 nm and Ex = 255-275 nm/Em = 425-455 nm. The results show that HA extracted from the refuse disposed in the year of 1989 was formed by connecting small-condensed aromatic structures with protein-like chains. Compared with HA extracted from the refuse disposed in the year of 1992, HA extracted from the refuse of 1996 had a higher fluorescence intensity and lower r_(B,A) (the ratio of the fluorescence intensities of peak B and peak A) value. It contained low molar mass components, low aromatic condensation degree, and more easily oxidized substituents. This indicates that the landfill time strongly affects the EEMs characteristics of HA, and that the humification degree of HA increases with the landfill time. A red shift to a longer wavelength region and an increase of fluorescence intensity were observed when the concentration of HA was increased, suggesting that concentration had a great influence on the fluorescence characteristics of HAs. pH (2-12) also had significant effects on the fluorescence intensity, although it exerted no effect on the peak position of fluorescence of HA and FA. The results of FRI show that increasing concentration lead to more interactions among various structure components and that small molecular weight units tend to aggregate or be masked into more complicated and larger structures. The pH influence on the fluorescence intensity of HA seems mainly through molecular configuration, while the fluorescence intensity change with pH may be due to various substituents of FA.     

Assessment of chemical and biochemical stabilization of organic C in soils from the long-term experiments at Rothamsted (UK)

Biological and chemical stabilization of organic C was assessed in soils sampled from the long-term experiments at Rothamsted (UK), representing a wide range of carbon inputs and managements by extracting labile, non-humified organic matter (NH) and humic substances (HS). Four sequentially extracted humic substances fractions of soil organic matter (SOM) were extracted and characterized before and after a 215-day laboratory incubation at 25 degrees C from two arable soils, a woodland soil and an occasionally stubbed soil. The fractions corresponded to biochemically stabilised SOM extracted in 0.5M NaOH (free fulvic acids (FA) and humic acids (HA)) and chemically plus biochemically stabilised SOM extracted from the residue with 0.1M Na4P2O7 plus 0.1M NaOH (bound FA and HA). Our aim was to investigate the effects of chemical and biochemical stabilization on carbon sequestration. The non-humic to humic (NH/H) C ratio separated the soils into two distinct groups: arable soils (unless fertilised with farmyard manure) had an NH/H C ratio between 1.05 and 0.71, about twice that of the other soils (0.51-0.26). During incubation a slow, but detectable, decrease in the NH/H C ratio occurred in soils of C input equivalent or lower to 4Mgha(-1)y(-1), whereas the ratio remained practically constant in the other soils. Before incubation the free to bound humic C ratio increased linearly (R2=0.91) with C inputs in the soils from the Broadbalk experiment and decreased during incubation, showing that biochemical stabilization is less effective than chemical stabilization in preserving humic C. Changes in delta13C and delta15N after incubation were confined to the free FA fractions. The delta13C of free FA increased by 1.48 and 0.80 per thousand, respectively, in the stubbed and woodland soils, indicating a progressive biological transformation. On the contrary, a decrease was observed for the bound FA of both soils. Concomitantly, a Deltadelta15N of up to +3.52 per thousand was measured after incubation in the free FA fraction and a -2.58 Deltadelta15N in the bound FA. These changes, which occurred during soil incubation in the absence of C inputs, indicate that free FA fractions were utilised by soil microorganisms, and bound FA were decomposed and replaced, in part, by newly synthesized FA. The 13CPMAS-TOSS NMR spectra of free HA extracted before and after 215 days of incubation were mostly unchanged. In contrast, changes were evident in bound HA and showed an increase in aromatic C after incubation.     

Study of the organic matter evolution during municipal solid waste composting aimed at identifying suitable parameters for the evaluation of compost maturity

In this work the composting process of municipal solid wastes was studied in order to characterize the transformations of organic matter, particularly humic acid (HA). A composting process, lasting three months, was monitored by chemical methods; the following parameters were measured: water-soluble carbon concentration (WSC) and humic substances content (humic and fulvic acid (FA)). The effects of humification on the molecular structure of humic acid (HA) were also evaluated by Fourier transform infrared (FT-IR) and (13)C NMR spectroscopy. WSC concentration rapidly increased reaching a maximum at day-14 of the composting process and then declined. The humic and fulvic acid content (HA and FA, respectively) slightly increased during the process. The FT-IR and (13)C NMR spectra of HA indicate a high rate of change in structure during composting. The groups containing aromatic and carboxylic C increased, while polysaccharides and other aliphatic structures degraded during composting, resulting in HA structures of higher aromaticity. Therefore, spectrometric measurements could provide information significantly correlated to conventional chemical parameters of compost maturity.     

Characterization and removal of dissolved organic matter (DOM) from landfill leachate rejected by nanofiltration

Dissolved organic matter (DOM) from wastewater rejected by nanofiltration from a landfill leachate treatment plant was fractionated into humic acid (HA), fulvic acid (FA) and hydrophilic (HyI) fractions. It was found that humic substances (HA and FA) composed 75% of the total dissolved organic carbon (DOC) concentration of the DOM, with an average molecular weight of about 1000 Da. Elemental analysis, infrared spectroscopy, UV-visible spectroscopy and acid-base titration observations showed that the HA and FA of the DOM exhibited lower fractions of condensed aromatic functional groups but larger fractions of acidic groups compared with other aquatic DOMs. The properties of HA and FA were similar, but HA exhibited more complete humification, while the HyI fraction had more acidic groups. An aminated polymeric adsorbent NDA-8 was used to adsorb the DOM in the wastewater along with primary coagulation. Results of bench-scale experiments indicated that the treatment process could effectively remove the DOM and heavy metals while desorption liquid was 10 times more condensed than raw wastewater. Results of desorption and reproducibility tests consolidated the strong application potential of this treatment process as an advanced landfill leachate treatment technology.     

Atmospheric emissions and attenuation of non-methane organic compounds in cover soils at a French landfill

In addition to methane (CH(4)) and carbon dioxide (CO(2)), landfill gas may contain more than 200 non-methane organic compounds (NMOCs) including C(2+)-alkanes, aromatics, and halogenated hydrocarbons. Although the trace components make up less than 1% v/v of typical landfill gas, they may exert a disproportionate environmental burden. The objective of this work was to study the dynamics of CH(4) and NMOCs in the landfill cover soils overlying two types of gas collection systems: a conventional gas collection system with vertical wells and an innovative horizontal gas collection layer consisting of permeable gravel with a geomembrane above it. The 47 NMOCs quantified in the landfill gas samples included primarily alkanes (C(2)-C(10)), alkenes (C(2)-C(4)), halogenated hydrocarbons (including (hydro)chlorofluorocarbons ((H)CFCs)), and aromatic hydrocarbons (BTEXs). In general, both CH(4) and NMOC fluxes were all very small with positive and negative fluxes. The highest percentages of positive fluxes in this study (considering all quantified species) were observed at the hotspots, located mainly along cell perimeters of the conventional cell. The capacity of the cover soil for NMOC oxidation was investigated in microcosms incubated with CH(4) and oxygen (O(2)). The cover soil showed a relatively high capacity for CH(4) oxidation and simultaneous co-oxidation of the halogenated aliphatic compounds, especially at the conventional cell. Fully substituted carbons (TeCM, PCE, CFC-11, CFC-12, CFC-113, HFC-134a, and HCFC-141b) were not degraded in the presence of CH(4) and O(2). Benzene and toluene were also degraded with relative high rates. This study demonstrates that landfill soil covers show a significant potential for CH(4) oxidation and co-oxidation of NMOCs.     

Characterization of wood plastic composites made from landfill-derived plastic and sawdust: Volatile compounds and olfactometric analysis

Application of wood plastic composites (WPCs) obtained from recycled materials initially intended for landfill is usually limited by their composition, mainly focused on release of volatile organic compounds (VOCs) which could affect quality or human safety. The study of the VOCs released by a material is a requirement for new composite materials. Characterization and quantification of VOCs of several WPC produced with low density polyethylene (LDPE) and polyethylene/ethylene vinyl acetate (PE/EVA) films and sawdust were carried out, in each stage of production, by solid phase microextraction in headspace mode (HS-SPME) and gas chromatography–mass spectrometry (GC–MS). An odor profile was also obtained by HS-SPME and GC–MS coupled with olfactometry analysis. More than 140 compounds were observed in the raw materials and WPC samples. Some quantified compounds were considered WPC markers such as furfural, 2-methoxyphenol, N-methylphthalimide and 2,4-di-tert-butylphenol. Hexanoic acid, acetic acid, 2-methoxyphenol, acetylfuran, diacetyl, and aldehydes were the most important odorants. None of the VOCs were found to affect human safety for use of the WPC.     

Molecular composition of recycled organic wastes,as determined by solid-state 13C NMR and elemental analyses

Using solid state ¹³C NMR data and elemental composition in a molecular mixing model, we estimated the molecular components of the organic matter in 16 recycled organic (RO) wastes representative of the major materials generated in the Sydney basin area. Close correspondence was found between the measured NMR signal intensities and those predicted by the model for all RO wastes except for poultry manure char. Molecular nature of the organic matter differed widely between the RO wastes. As a proportion of organic C, carbohydrate C ranged from 0.07 to 0.63, protein C from <0.01 to 0.66, lignin C from <0.01 to 0.31, aliphatic C from 0.09 to 0.73, carbonyl C from 0.02 to 0.23, and char C from 0 to 0.45. This method is considered preferable to techniques involving imprecise extraction methods for RO wastes. Molecular composition data has great potential as a predictor of RO waste soil carbon and nutrient outcomes.     

Qualitative and Quantitative Analysis of Lignin Produced from Beech Wood by Different Conditions of the Organosolv Process

Lignins in general have been extensively studied, while beech wood lignin in particular is rarely researched. In the present work, Organosolv isolated lignin from beech wood (OBL) has been characterized. The isolation was done by two methods: (a) by using sulfuric acid at 170 °C and a reaction time of 120 min and (b) at a temperature of 180 °C for 240 min. A range of analytical methods were applied including elemental analysis, FT-IR, UV–Vis, ³¹P NMR, SEC, Pyrolysis-GC/MS and HPLC to gain information about establish the purity, structure, molecular weight, thermal behavior and to determine carbohydrate residues according to the NREL protocol. FT-IR and UV–Vis spectra of OBL revealed expected typical absorptions for lignins. NREL analysis presented a carbohydrate-free lignin fraction which has not been achieved to date. TGA and DSC are used to study the thermal behavior of the isolated lignins and showed a relatively low glass transition temperatures (T_g: 123 °C) and decomposition temperatures of 348 and 381 °C. The pyrograms generated from the pyrolysis–GC/MS at 550 °C consisted mainly of fragments of syringyl, guaiacyl and hydroxyphenyl units, thereby confirming the results of the NMR analysis. Our findings support Organolsolv as an efficient method to isolate pure lignin fractions from beech wood with practical value in industry.     

Evolution of organic matter during composting of different organic wastes assessed by CPMAS 13C NMR spectroscopy

In this paper, the evolution of organic matter (OM) during composting of different mixtures of various organic wastes was assessed by means of chemical analyses and CPMAS ¹³C NMR spectroscopy measured during composting. The trends of temperatures and C/N ratios supported the correct evolution of the processes. The CPMAS ¹³C NMR spectra of all composting substrates indicated a reduction in carbohydrates and an increase in aromatic, phenolic, carboxylic and carbonylic C which suggested a preference by microorganisms for easily degradable C molecules. The presence of hardly degradable pine needles in one of the substrates accounted for the lowest increase in alkyl C and the lowest reduction in carbohydrates and carboxyl C as opposite to another substrate characterized by the presence of a highly degradable material such as spent yeast from beer production, which showed the highest increase of the alkyl C/O-alkyl C ratio. The highest increase of COOH deriving by the oxidative degradation of cellulose was shown by a substrate composed by about 50% of plant residues. The smallest increases in alkyl C/O-alkyl C ratio and in polysaccharides were associated to the degradation of proteins and lipids which are major components of sewage sludge. Results obtained were related to the different composition of fresh organic substrates and provided evidence of different OM evolution patterns as a function of the initial substrate composition.     

Modification of soil humic matter after 4 years of compost application

Two soil plots, 1 ha each, were amended yearly for 4 years, respectively, with 35.8 and 71.6 Mg ha(-1) yr(-1) of mature compost (CM) obtained from food and vegetable residues. The compost, amended soils, and a control soil plot after 4 years (S4), were analyzed for humin (HUC), humic acid (HAC), fulvic acid (FAC), and non-humic carbon (NHC) content. Compared to S4, the amended soil contained more humified C (HAC, FAC and HUC) and less NHC. Further evidence of the effect of compost on soil organic matter was obtained by the analysis of the humic acid (HA) fractions isolated from both the compost and the soils. These were characterized by elemental analyses and Diffuse Reflectance Infrared Fourier Transformed spectroscopy. The HAs isolated from CM and from S4 were significantly different. The HAs isolated from the amended plots were more similar to HA isolated from CM than to HA isolated from S4. The experimental data of this work indicate that the compost application may affect significantly the soil organic matter composition, and that the approach used in this work allows one to trace the fate of compost organic matter in soil.     

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of 29Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research on the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique.     

A Methodology to Identify the Releasing of the Amide-Containing β-Glucan from the Usnea Lichen: A Spectroscopic Study

Journal of Polymers and the Environment - Polymer fractions from a biological matrix have been well-characterized by vibrational spectroscopy, XPS, CP/MAS&nbsp;13C NMR, MALDI-TOF mass...     

Hydrodechlorination/detoxification of PCDDs,PCDFs, and co-PCBs in fly ash by using calcium polysulfide

Dioxins like polychlorinated dibenzo-p-dioxins (PCSDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are mainly emitted from waste incinerators (WIs) and have become an international research focus because of its serious concerns over the adverse health effects. The detoxification of PCCDs/Fs and PCBs is very difficult because of their stable chemical structure. A significant hydrodechlorination/detoxification of polychlorinated 1-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were achieved in fly ash by using an aqueous mixture of calcium hydroxide and sulfur. Two different fly ashes were studied: originating from municipal waste incinerator (FA1) and industrial waste incinerator (FA2). They were heated with the aqueous mixture at 150 °C for 30 or 60 min with agitation. Higher decomposition (87%) and detoxification (87.7%) of PCDD/Fs and PCBs were achieved at 150 °C with two runs; every run was for 30 min, compared to one run for 60 min. FA2 gave higher decomposition and detoxification as compared to FA1, which might be due to higher metal content that played a catalytic role to decompose and detoxify the PCDDs, PCDFs and PCBs. The decomposition and detoxification of PCDFs in fly ash was higher than PCDDs and was augmented with increasing number of chlorides on aromatic compounds. As the highly significant decomposition and detoxification of higher concentration of PCDD/Fs and PCBs were achieved in 1 hour without additive catalyst and at low temperature of 150 °C, therefore, the developed method is cost effective and most suitable to apply on commercial/industrial level. The detail results of hydrodechlorination/detoxification of PCDD, PCDFs at different conditions are described and its mechanism is discussed.     

Adsorbable organic halides (AOX), AOX formation potential, and PCDDs/DFs in landfill leachate and their removal in water treatment processes

Adsorbable organic halides (AOX) and AOX formation potential (AOXFP) were investigated in 46 landfill lea-chates as potentially toxic parameters. AOX in landfill leachate was within the range <10–2200 μg Cl/l, and AOXFP was within 51–15 000 μg Cl/l. AOX and AOXFP correlated with chemical oxygen demand (COD). AOX discharge from closed landfills was generally lower than that from operating landfills. The molar ratio of AOXFP/total organic carbon (TOC) suggested that organic compounds in a leachate have a double bond every 15–190 carbons under the supposition that one chlorine would add to one double bond. The five landfills discharging high-level AOXFP (>4000 μg Cl/l) were all landfills where sludge had been dumped. The removal efficiencies of three parameters through leachate treatment processes were as follows: polychlorinated dibenzo-dioxins/dibenzo-furans (PCDDs/DFs) > TOC > AOX. PCDDs/DFs were substantially removed at p.p.t. levels, while AOX was hardly removed at relatively low levels. Received: February 14, 2000 / Accepted: January 9, 2001     

CHANGES IN MAJOR AND TRACE COMPONENTS OF LANDFILL GAS DURING SUBSURFACE MIGRATION

A gas plume emanating from the Foxhall Landfill in Suffolk (U.K.) has been defined within unsaturated ferruginous sands on the basis of elevated concentrations of methane, carbon dioxide and volatile organic compounds (VOCs). The plume is relatively narrow, extends more than 100 m from the landfill boundary, and lies mainly between 2 m bgl (below ground level) and the water table at 9.5 m bgl. With increasing distance along the axis of the plume, the ratio of methane to carbon dioxide gradually decreases, while nitrogen increases. Oxygen appears beyond 80 m from the landfill boundary. Stable carbon and hydrogen isotope ratios in methane become heavier with distance, while carbon dioxide becomes isotopically lighter with respect to stable carbon. This provides strong evidence for microbially mediated methane oxidation. Zones of black reduced sediment near the landfill suggest that ferric iron [Fe(III)] may be acting as an electron acceptor for oxidation. No thermal anomaly was observed, thus suggesting that the rate of oxidation/flux of methane is low. Volatile organic compounds in the plume were trapped using a combination of sorbants (Tenax GR, Haysep Q and Carbosieve S-III), and desorbed thermally into a GC/MS for semi-quantitative analysis. The 79 VOCs identified were similar to those found in other landfills, and their concentrations, both in the landfill and in the soil gas, were broadly related to their volatility. Only two compounds (vinyl chloride and dichlorofluoromethane) approached or exceeded the long-term exposure limit (LTEL, as defined by the U.K. Health and Safety Executive, 1992) outside the landfill. Halogenated compounds (dichlorodifluoromethane, dichlorofluoromethane and trichlorofluoromethane) were found to be most mobile but their concentration profiles suggest that they may have been flushed out of the landfill during its early stages. It is suggested that the association of volatile halogenated compounds with methane is good evidence that they are derived from a landfill.     

Functional changes in culturable microbial communities during a co-composting process: Carbon source utilization and co-metabolism

Microbial communities in sewage sludge and green waste co-composting were investigated using culture-dependent methods and community level physiological profiles (CLPP) with Biolog Microplate. Different microbial groups characterized each stage of composting. Bacterial densities were high from beginning to end of composting, whereas actinomycete densities increased only after bio-oxidation phase i.e. after 40 days. Fungal populations become particularly high during the last stage of decomposition. Cluster analyses of metabolic profiles revealed a similar separation between two groups of composts at 67 days for bacteria and fungi. Principal component analysis (PCA) applied to bacterial and fungal CLPP data showed a chronological distribution of composts with two phases. The first one (before 67 days), where the composts were characterized by the rapid decomposition of non-humic biodegradable organic matter, was significantly correlated to the decrease of C, C/N, organic matter (OM), fulvic acid (FA), respiration, cellulase, protease, phenoloxidase, alkaline and acid phosphatases activities. The second phase corresponding to the formation of polycondensed humic-like substances was significantly correlated to humic acid (HA) content, pH and HA/FA. The influent substrates selected on both factorial maps showed that microbial communities could adapt their metabolic capacities to the particular environment. The first phase seems to be focused on easily degradable substrate utilization whereas the maturation phase appears as multiple metabolisms, which induce the release of metabolites and their polymerization leading to humification processes.     

Chemical characterization of landfill leachates--400 parameters and compounds

A large number of hazardous compounds can be expected to be present in landfill leachates, many of which have not yet been identified. Thus this study screened samples from 12 Swedish municipal landfill sites for 400 parameters and compounds. More than 90 organic and metal organic compounds and 50 inorganic elements were detected, some of which seem to have not been detected before. Compounds detected include halogenated aliphatic compounds, benzene and alkylated benzenes, phenol and alkylated phenols, ethoxylates, polycyclic aromatic compounds, phthalic esters, chlorinated benzenes, chlorinated phenols, PCB, chlorinated dioxins and chlorinated furans, bromated flame-retardants, pesticides, organic tin, methyl mercury and heavy metals. The presence of this large number of hazardous compounds in landfill leachates should have a significant impact on future landfill risk assessments and the development of leachate treatment methods. We propose that future research should pay more attention to the metal-organic and organic compounds detected in this study. We also suggest using leachate sediments as a matrix for detecting hydrophobic compounds, and reflecting on the degradation phase when evaluating results from monitoring studies. The extensive compilation of compounds in this paper can be used to select compounds to search for in future studies.     

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ¹³C, δ²H and δ¹⁸O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration.We found significant differences in the δ¹³C-value of the dissolved inorganic carbon (δ¹³C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ¹³C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ¹³C-DIC of ?20‰ to ?25‰. The production of methane under anaerobic conditions caused an increase in δ¹³C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ¹³C-DIC of about ?20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation–reduction status of MSW landfills.Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration.     

Carbon speciation in municipal solid waste incinerator (MSWI) bottom ash in relation to facilitated metal leaching

The release of inorganic and organic contaminants from municipal solid waste incinerator (MSWI) bottom ash is controlled to a large extent by the release of dissolved organic carbon (DOC), and in particular by the reactive humic (HA) and fulvic acids (FA) subfractions of DOC. The properties of organic matter contributing to the release of DOC, HA and FA are, therefore, important for environmental risk assessment. In this study we have quantitatively measured the carbon speciation, and its relation with the leaching of Cu, in three fresh and carbonated MSWI bottom ash samples. Results show that up to only 25% of loss on ignition (LOI) consists of organic carbon (OC), while about 17% of OC in the three samples consists of HA and FA. Up to 50% of DOC in MSWI bottom ash leachates was identified as fulvic acid (FA). This value is substantially higher than previously estimated for these MSWI bottom ash samples and is consistent with the higher recovery of the new method that was applied. The results of this study imply that methods focusing on specific carbon fractions are more appropriate for assessment of environmentally relevant organic carbon species than the measurement of LOI.     

Soil contamination by halogenated polycyclic aromatic hydrocarbons from open burning of e-waste in Agbogbloshie (Accra,Ghana)

Detailed composition of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) generated during informal recycling of e-waste and their toxic relevance are still poorly understood. This study investigated the occurrence of Cl-PAHs and Br-PAHs in surface soil samples from the Agbogbloshie e-waste recycling site (Accra, Ghana) using quantitative gas chromatography–mass spectrometry (GC–MS) and comprehensive two-dimensional GC–time-of-flight mass spectrometry (GC × GC–ToFMS) profiling. The results of GC–MS analysis showed elevated concentrations in open e-waste burning areas (160–220 and 19–46 ng/g dry weight for Cl- and Br-PAHs, respectively) with substantial contribution from unidentified compounds (respectively, more than 36 and 70%, based on the total areas of potential peaks). Cl- and Br-PAHs from e-waste burning had a distinctive composition dominated by ring–ring compounds. Several homologue groups not monitored with GC–MS were found using GC × GC–ToFMS: PAHs with up to 5Cl or 3Br, mixed halogenated PAHs and chlorinated methylPAHs. The dioxin-like toxic equivalents of the identified Cl-/Br-PAHs in soils, estimated from their in vitro AhR agonist potencies relative to 2,3,7,8-tetrachlorodibenzo-p-dioxin, were much lower than the range reported for chlorinated and brominated dioxins. However, the toxicity of the unidentified halogenated PAHs remained unclear.