Leaching of brominated flame retardants in leachate from landfills in Japan

Leachate samples were taken from seven different landfills and concentrations of brominated flame retardants (BFRs), i.e. polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), were quantified. Leaching characteristics of BFRs, especially factors affecting leachability, were clarified to obtain basic information regarding the release of BFRs into the environment. The results obtained for observed levels of the sum of PBDE-47, -99 and -100 were n.d.--4000 pg/l for the raw leachate and n.d. for the treated one, respectively, and those of TBBPA were n.d.--620,000 pg/l for the raw leachate and n.d.--11,000 pg/l for the treated one, respectively. Three sites that not only had crushed material from bulk wastes such as waste electric and electronic equipment, but also were under operation or within a year since closure, indicated a higher concentration of BFRs than the other sites. In particular extremely high concentration of PBDEs was observed at a site with a large amount of organics. Considering the leaching characteristics of BFRs, there exists the possibility that leachability of PBDEs is influenced by the presence of dissolved humic matter (DHM) in the leachate. The high removal efficiency for BFRs in the leachate treatment process was also confirmed.     

Effect of dissolved humic matters on the leachability of PCDD/F from fly ash--laboratory experiment using Aldrich humic acid

The effect of dissolved humic matters (DHM) on the leachability of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) in fly ash was studied theoretically and in laboratorial condition to verify the previous results for pilot and field experiment of incineration residues landfill. In theoretical review, it was shown that DHM could influence the actual solubility and leachability of PCDD/F. The higher concentration of DHM showed the higher leachability of PCDD/F. In the leaching test, three different DHM concentrations and pHs of solutions were adopted to fly ash samples imaging the various characteristics of municipal solid waste leachate. It was proved experimentally that the leachability of PCDD/F increased with increasing DHM concentration in all pH conditions. The highest leachability was shown at the highest pH. Isomer distribution patterns of PCDD/F in all leachates were similar in all pH conditions. It backed up the distribution theory of PCDD/F between DHM and water.     

Distribution and temporal trend of polybrominated diphenyl ethers in one Shanghai municipal landfill, China

The scarcity of information on polybrominated diphenyl ethers’ (PBDEs) flow in landfill restricts the life cycle analysis of PBDEs. In this study, eight PBDE congeners (BDEs 28, 47, 99, 100, 153, 154, 183, and 209) in topsoil, vegetation leaves, leachate, and municipal aged refuse collected from Shanghai Laogang Municipal Landfill (SLML) were investigated. The present study revealed elevated PBDE concentrations in topsoil and proved PBDE leakage from SLML and vegetation uptake. BDE-209 was the predominant congener, and this could be due to massive usage of deca-BDE mixture in Shanghai. ΣPBDE concentrations in leachates treated by reed wetland and A²/O process fell in the low end of the worldwide range. ΣPBDE concentrations in aged refuse samples rose from under 50 ng/g dw in 1989 to the range of 5,150–5,718 ng/g dw in 2002. PBDE concentrations increase in aged refuse samples throughout the 1990s into the 2000s paralleled municipal solid waste output from 1991 to 2002 in Shanghai. Exponential increase in BDE-209 concentration in aged refuse suggested the increasing market demands for deca-BDE mixture after 1990 in China. Notably, the inventory of PBDEs in SLML was 28.7 MT, and the doubling time of BDE-209 in aged refuse was calculated to be 1.6 year. SLML can be considered as a source of PBDE and one main recipient of PBDE as well, receiving inputs predominantly from the PBDE-containing waste. Priority should be given to formulate regulation on PBDEs and sorting work before landfill disposal.     

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans from raw and solidified waste incineration residues

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from raw and solidified air pollution control (APC) residues were examined via a nine-time multiple leaching test. The effect of injected activated carbon in the APC residues on the PCDD/F leachability was also evaluated. When humic acid solution was used as a leachant, the leaching concentrations of PCDD/Fs fluctuated between the first and the fifth leaching, followed by a gradual increase and then suddenly reached maximum values at the leaching sequences around seventh and eighth. This significant enhancement in PCDD/F leachability was mainly due to an increase in the release of highly chlorinated PCDD/Fs. Leaching of PCDD/Fs with n-hexane was, in contrast, primarily caused by the partitioning of hydrophobic PCDD/Fs between the APC residue surface and the liquid phase of n-hexane. Consequently, the largest leaching concentrations for n-hexane tests achieved at the first leaching, followed by a decrease and reached plateaus. Solidification/stabilization (S/S) decreased the PCDD/F leachability up to the fifth leaching by the use of humic acid solution. However, S/S increased the PCDD/F leaching concentrations and rates with n-hexane. The activated carbon in APC residues significantly inhibited the release of PCDD/F with n-hexane. The inhibiting effect provided by activated carbon was, however, less significant by the use of humic acid solution.     

A pilot and field investigation on mobility of PCDDs/PCDFs in landfill site with municipal solid waste incineration residue

A field investigation by boring was carried out in a landfill site primarily with municipal solid waste incineration residue. From the collected core samples, vertical profiles of homologous content of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in the landfill layer were traced and the behavior of PCDDs/PCDFs was examined. In addition, a pilot-scale study was conducted on the PCDDs/PCDFs leached from incineration fly ash and the treated one using large landfill simulation columns (lysimeters) and the leaching behavior of PCDDs/PCDFs was examined. As a result, it was found that the coexistence of dissolved coloring constituents (DCCs), which might be composed of constituents like dissolved humic matters having strong affinity for hydrophobic organic pollutants, could enhance the leachability of PCDDs/PCDFs, thus contributing to the vertical movement and leaching behavior of PCDDs/PCDFs in the landfill layers of the incineration residue. Moreover, it is highly probable that DCCs derive from the unburned carbon in the bottom ash mixed and buried with the fly ash containing a high content of PCDDs/PCDFs.     

PBDEs in leachates from municipal solid waste dumping sites in tropical Asian countries: phase distribution and debromination

Polybrominated diphenyl ethers (PBDEs) are extensively used as flame retardants in many consumer products, and leachates from landfills have been identified as one of the possible sources of PBDEs in the environment. Meanwhile, the unprecedented economic and population growths of some Asian countries over the last decade have led to significant increases in the amount of waste containing PBDEs in that region. This study investigates the status of PBDEs in leachates from municipal solid waste dumping sites (MSWDS) in tropical Asian countries. A total of 46 PBDE congeners were measured, both in the adsorbed (n?=?24) and dissolved (n?=?16) phases, in leachate samples collected, from 2002 to 2010, from ten MSWDS distributed among the eight countries of Lao PDR, Cambodia, Vietnam, India, Indonesia, Thailand, the Philippines, and Malaysia. PBDEs were predominantly found in the adsorbed phase. Partitioning of PBDEs in the dissolved phase was associated with the presence of dissolved organic matter; the apparent organic carbon-normalized partition coefficients (K′_oc) of the BDE congeners were lower by two to four orders of magnitude than the K _oc predicted from the octanol–water partition coefficients (K _ow). The total PBDE concentrations from mono- to deca-BDEs ranged from 3.7 to 133,000 ng/L, and showed a trend toward higher concentrations in the more populous and industrialized Asian countries. The congener profiles in the leachates basically reflected the composition of PBDE technical mixtures. The occurrence of congeners not contained, or in trace concentrations, in technical products (e.g., BDEs 208, 207, 206, 202, 188, 179, 49, 17/25, 8, 1) was observed in most of the leachate samples, suggesting the debromination of technical mixtures, including BDE-209, in the MSWDS of tropical Asian countries. Moreover, the temporal trend indicated the reduction of BDE-209 over time, with a corresponding increase in and/or emergence of lower brominated PBDE congeners. The results indicated that MSWDS of tropical Asian countries are potential sources of environmental PBDEs, which may be transported to the aquatic environment via dissolution with dissolved organic matter. MSWDS could be amplifiers of PBDE toxicity in the environment, possibly through debromination.     

Assessment of polybrominated diphenyl ethers in eggs of waterbirds from South China

Concentrations of total polybrominated diphenyl ethers (PBDEs) in Ardeid eggs from Hong Kong, Xiamen and Quanzhou in south China ranged from 140-1000, 30-550 and 140-380ngg(-1), lipid wt., respectively. There were spatial and interspecies variations in the abundance and congeneric profiles of PBDEs. The different congeneric profiles observed among the study sites may be associated with the developmental phases of the cities, as well as a possible consequence of debromination of BDE209. Marked concentrations of higher-brominated diphenyl ethers (BDEs 183, 196, 197, 206, 207 and 209) were detected in the egg samples from all sites, probably indicating uptake of BDE209 by top predators, and that there is widespread occurrence of BDE209 in south China. Comparisons of egg concentrations of BDEs 47, 99, 153 and 209 with tentative critical concentrations for neurobehavioral effects and oxidative stress indicated some potential risks for BDE99 and BDE209 in the Ardeid populations.     

Leaching characteristics of PCDDs/DFs and dioxin-like PCBs from landfills containing municipal solid waste and incineration residues

To investigate the leaching characteristic of persistent organic pollutants (POPs), such as non-ortho and mono-ortho substituted chlorobiphebyls (dioxin-like PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), in leachate from municipal solid waste (MSW) landfill sites containing incineration residues, raw leachate samples were collected twice from 12 selected MSW landfill sites. The samples were divided into their liquid and solid phases using GF/B (pore size 1.0 microm), and the concentrations of POPs then determined. The concentrations of PCDDs/DFs ranged from 0.65 to 5.88 pg-TEQ/l (average 2.86 pg-TEQ/l), and those of dioxin-like PCBs from 0.05 to 0.32 pg-TEQ/l (average 0.18 pg-TEQ/l). The major congeners of leached PCDDs/DFs and dioxin-like PCBs in liquid and solid phases were OCDD (about 60%), 2,3',4,4',5-PeCBs (about 30%), and 2,3,4,4',5-PeCBs (about 54%). The relationship between landfill age and the leaching concentration of PCDDs/DFs, and effects of dissolved organic carbon (DOC) on the leaching of PCDDs/DFs are also discussed. Finally, a leaching prediction model of PCDDs/DFs from MSW landfills has been suggested using parameters, such as hydrophobic neutral organic carbons, total dissolved solid, and the ratio of non-biodegradable wastes in landfill sites.     

Arsenic leachability and speciation in cement immobilized water treatment sludge

Arsenic leachability and speciation in cement immobilized water treatment sludge were investigated with leaching tests and X-ray absorption near edge structure (XANES) spectroscopy. The As leachability in the sludge determined with the toxicity characteristic leaching procedure (TCLP) and the waste extraction test (WET) was 283 and 7490 microgl(-1), respectively. Extractions with a lower liquid to solid ratio, under anaerobic conditions, and using citric acid buffer solution dramatically increased the leachate As concentration. XANES results showed that the As(III) composition was reduced from 51.1% of the total As content in the sludge to 16.3% in the cement treated sample with 28 days of cure. When the cement treated sample was cured for two years, the As(III) composition was decreased to 7.4%. The cement treatment reduced the As leachability. The leachate As(III) and total As concentrations were of the same order of magnitude in the samples cured for 28 days as for 2yr. However, consistently lower concentrations were detected in samples with longer cure time. The results of this study improve our understanding of arsenic speciation and leachability in the cement matrix after long cure times.     

MBR-NF截留液中腐植酸的纳滤分离浓缩特性

MBR-NF截留液是一类难处理的高浓度有机废水,其所含有机物几乎都是腐植酸,可考虑资源利用。实验室内采用纳滤对其所含腐植酸进行分离浓缩。引入分离因子来表征纳滤的分离效果。实验结果表明,分离因子(SF)与体积浓缩倍数(CF)有很好的线性关系,浓缩倍数为5时,截留液中有机碳浓度为9 413 mg/L,重金属浓度处于mg/L水平,分离因子达到2.76,表明纳滤可有效地将MBR-NF截留液中的腐植酸与无机盐分离,并进行浓缩。     

Leaching characteristics of polycyclic aromatic hydrocarbons (PAHs) from spiked sandy soil

In order to evaluate the factors affecting leachability of hydrophobic organic pollutants (HOPs), we performed leaching tests under a variety of conditions using sandy soil contaminated with phenanthrene and pyrene. The results obtained were: (1) the shaking time, temperature, and dissolved humic matter (DHM, as coexisting matter) increased leachability; (2) ionic strength reduced leachability; and (3) the liquid-to-solid ratio and pH level had no effect on leaching concentration of HOPs. In DHM-added leaching tests assuming equilibrium with HOPs, DHM, and solid matrix, the partitioning (binding) coefficient of HOPs to DHM was accurately calculated with the equations proposed in this study. While we recommend taking into consideration the coexistence of DHM, it is difficult to use universally because its properties differ according to origin and extracting method. It is therefore reasonable to use an alternative reagent having an effect similar to that of DHM.     

Catalytic and electrocatalytic hydrogenolysis of brominated diphenyl ethers

Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental contaminants due to their use as additive flame-retardants. Conventional catalytic hydrogenolysis in methanol solution and electrocatalytic hydrogenolysis in aqueous methanol were examined as methods for debrominating mono- and di-bromodiphenyl ethers, as well as a commercial penta-PBDE mixture, in each case using palladium on alumina as the catalyst. Electrocatalytic hydrogenolysis employed a divided flow-through batch cell, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes. Both methods gave efficient sequential debromination, with essentially complete removal of bromine from the PBDEs, but the electrocatalytic method was limited by the poor solubility of PBDEs in aqueous methanol.     

Heavy metals in urban soils of East St. Louis, IL. Part II: Leaching characteristics and modeling

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.     

Evaluation of the stability of arsenic immobilized by microbial sulfate reduction using TCLP extractions and long-term leaching techniques

An investigation was conducted to evaluate the stability or leachability of arsenic immobilized by microbial sulfate reduction. Anoxic solid-phase samples taken from a bioreactor previously used to treat metal and As contaminated water using sulfate reducing bacteria (SRB) were subjected to the toxicity characteristic leaching procedure (TCLP) and long-term column leaching tests. The results from TCLP experiments showed that the concentration of As leached from solid-phase sulfide material (SSM) samples after an 18 h extraction time was <300 microgl(-1), which is below the current maximum Australian TCLP leachate value for As, and thus would not be characterized as a hazardous waste. In terms of percent total As leached, this was equivalent to <8.5% for SSM samples initially containing 61.3 mgkg(-1) As. The levels of As extracted by the TCLP was found to be significantly lowered or underestimated in the presence of dissolved oxygen, with As concentrations increasing with decreasing headspace-to-leachant volume ratios. The concentration of As was also consistently higher in nitrogen purged extractions compared to those performed in air. This was attributed to the dissolution of Fe-sulfide precipitates and subsequent oxidation of Fe(II) ions and precipitation of ferric(hydr)oxides, resulting in the adsorption of soluble As and corresponding decrease in As concentrations. According to the experimental data, it is recommended that TCLP tests for As leachability should be performed at least in zero-headspace vessels or preferably under nitrogen to minimize the oxidation of Fe(II) to ferric(hydr)oxides. In long-term leaching studies (approximately 68 days), it was found that the low solubility of the SSM ensured that rate of release of As was relatively slow, and the resulting leachate concentrations of As were below the current Australian guideline concentration for arsenic in drinking water.     

Mobility of Pb, Cu, and Zn in the phosphorus-amended contaminated soils under simulated landfill and rainfall conditions

Phosphorus-bearing materials have been widely applied in immobilization of heavy metals in contaminated soils. However, the study on the stability of the initially P-induced immobilized metals in the contaminated soils is far limited. This work was conducted to evaluate the mobility of Pb, Cu, and Zn in two contrasting contaminated soils amended with phosphate rock tailing (PR) and triple superphosphate fertilizer (TSP), and their combination (P?+?T) under simulated landfill and rainfall conditions. The main objective was to determine the stability of heavy metals in the P-treated contaminated soils in response to the changing environment conditions. The soils were amended with the P-bearing materials at a 2:1 molar ratio of P to metals. After equilibrated for 2 weeks, the soils were evaluated with the leaching procedures. The batch-based toxicity characteristic leaching procedure (TCLP) was conducted to determine the leachability of heavy metals from both untreated and P-treated soils under simulated landfill condition. The column-based synthetic precipitation leaching procedure (SPLP) were undertaken to measure the downward migration of metals from untreated and P-treated soils under simulated rainfall condition. Leachability of Pb, Cu, and Zn in the TCLP extract followed the order of Zn?>?Cu?>?Pb in both soils, with the organic-C- and clay-poor soil showing higher metal leachability than the organic-C- and clay-rich soil. All three P treatments reduced leachability of Pb, Cu, and Zn by up to 89.2, 24.4, and 34.3 %, respectively, compared to the untreated soil, and TSP revealed more effectiveness followed by P?+?T and then PR. The column experiments showed that Zn had the highest downward migration upon 10 pore volumes of SPLP leaching, followed by Pb and then Cu in both soils. However, migration of Pb and Zn to subsoil and leachate were inhibited in the P-treated soil, while Cu in the leachate was enhanced by P treatment in the organic-C-rich soil. More than 73 % P in the amendments remained in the upper 0–10 cm soil layers. However, leaching of P from soluble TSP was significant with 24.3 % of P migrated in the leachate in the organic-C-poor soil. The mobility of heavy metals in the P-treated soil varies with nature of P sources, heavy metals, and soils. Caution should be taken on the multi-metal stabilization since the P amendment may immobilize some metals while promoting others’ mobility. Also, attention should be paid to the high leaching of P from soluble P amendments since it may pose the risk of excessive P-induced eutrophication.     

Leaching behaviour of wood treated with creosote

The results of a laboratory investigation on the leaching behaviour of wood treated with creosote and of untreated wood are reported. A special leaching test derived from the German standard method DEV S4 test (DIN 38414) has been developed. Samples were leached in deionized water, in a solution buffered at pH 4.7 and in a solution of humic substances. The organic fraction of the leachate was extracted using liquid-liquid extraction. The extracts were analysed qualitatively with GC/MSD and quantified with GC/FID. The results were compared with those of Soxhlet-extracts from creosote-treated wood.     

Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface

The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.     

Effects of injected activated carbon and solidification treatment on the leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans from air pollution control residues of municipal waste incineration

To assess the effectiveness of the injected activated carbon, cement, and sulfur-containing chelating agent in controlling polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) release from the surface of air pollution control (APC) residues, this study examined the leachability of PCDD/Fs from APC residues generated by municipal solid waste incinerators. Results showed that PCDD/Fs were stably retained in the APC residues when the samples were leached with acetic acid solution. Highly chlorinated PCDD/F homologues (i.e., hepta- and octa-CDDs and CDFs) were relatively easy to leach. The leaching percentages of PCDD/Fs from raw APC residue samples containing activated carbon were smaller than those from samples without activated carbon, especially when n-hexane was used as the leachant. These results indicate that the flue gas injected activated carbon not only controls PCDD/F emissions, but also suppresses the leachability of PCDD/Fs from the APC residues. Solidification/stabilization (S/S) processes with 30wt% cement and 5wt% sulfur-containing agent can additionally decrease the leachability of PCDD/Fs with humic acid. Using n-hexane as the leachant, S/S processes increased the leachability of PCDD/Fs. Various low chlorinated PCDD/F congeners were moreover leached out of the APC residue samples, markedly increasing the leachate toxicity. The enhancement of leachability and toxicity owing to S/S processes may negatively impact the environment when APC residues are exposed to nonpolar organic solvents.     

Molecular orbital studies on brominated diphenyl ethers. Part II--reactivity and quantitative structure-activity (property) relationships

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic reactions of BDEs was predicted. Furthermore, satisfactory quantitative structure-activity (property) relationship (QSAR and QSPR) models were derived to calculate gas chromatographic and ultraviolet spectral properties and luciferase induction activities from the AM1-computed electronic parameters.     

Heavy Metals in Urban Soils of East St. Louis,IL Part II: Leaching Characteristics and Modeling

ABSTRACT

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.