Release of fluorocarbons from insulation foam in home appliances during shredding

It is a current practice that refrigerators and freezers in many countries are shredded after the end of useful lives. The shredder residue is deposited in landfills. During the shredding process a significant fraction of blowing agent (BA) in the insulation foam may be released into the atmosphere. The objective of this study is to determine the fraction of BA released from foam during shredding, by comparing the BA content in insulation foam of refrigerator units before shredding with the BA content of shredded foam. All foam samples analyzed were manufactured with trichlorofluoromethane [CFC-11 (CCl3F)] as BA. The average content of BA in the insulation foam from eight U.S. refrigerator units manufactured before 1993 was found to be 14.9% +/- 3.3% w/w. Several refrigerator units also identified as being manufactured before 1993 were stockpiled and shredded at three shredder facilities, of which one was operated in both wet and dry modes. The selected shredder facilities represent typical American facilities for shredding automobiles, refrigerators, freezers, and other iron containing waste products. Shredded material was collected and separated on location into four particle size categories: more than 32 mm, 16-32 mm, 8-16 mm, and 0-8 mm. Adjusting for sample purity, it was found that the majority (>81%) of the foam mass was shredded into particles larger than 16 mm. The smallest size fraction of foam (0-8 mm) was found to contain significantly less BA than the larger size categories, showing that up to 68% +/- 4% of the BA is released from these fine particles during the shredding process. Because only a minor fraction of the foam is shredded into particles smaller than 8 mm, this has a minor impact on the end result when calculating the total BA release from the shredding process. Comparing BA content in shredded samples from the three shredder facilities with the measured average BA content of the eight refrigerator units, it was found that on average 24.2% +/- 7.5% of the initial BA content is released during the shredding process.     

Release of Fluorocarbons from Insulation Foam in Home Appliances during Shredding

Abstract

It is a current practice that refrigerators and freezers in many countries are shredded after the end of useful lives. The shredder residue is deposited in landfills. During the shredding process a significant fraction of blowing agent (BA) in the insulation foam may be released into the atmosphere. The objective of this study is to determine the fraction of BA released from foam during shredding, by comparing the BA content in insulation foam of refrigerator units before shredding with the BA content of shredded foam. All foam samples analyzed were manufactured with trichlorofluoromethane [CFC-11 (CCl₃F)] as BA. The average content of BA in the insulation foam from eight U.S. refrigerator units manufactured before 1993 was found to be 14.9% ± 3.3% w/w. Several refrigerator units also identified as being manufactured before 1993 were stockpiled and shredded at three shredder facilities, of which one was operated in both wet and dry modes. The selected shredder facilities represent typical American facilities for shredding automobiles, refrigerators, freezers, and other iron containing waste products. Shredded material was collected and separated on location into four particle size categories: more than 32 mm, 16–32 mm, 8–16 mm, and 0–8 mm. Adjusting for sample purity, it was found that the majority (>81%) of the foam mass was shredded into particles larger than 16 mm. The smallest size fraction of foam (0–8 mm) was found to contain significantly less BA than the larger size categories, showing that up to 68% ± 4% of the BA is released from these fine particles during the shredding process. Because only a minor fraction of the foam is shredded into particles smaller than 8 mm, this has a minor impact on the end result when calculating the total BA release from the shredding process. Comparing BA content in shredded samples from the three shredder facilities with the measured average BA content of the eight refrigerator units, it was found that on average 24.2% ± 7.5% of the initial BA content is released during the shredding process.     

Biogeochemistry of benz(a)anthracene at the sediment-water interface

Two recirculating microcosms were used to study the fate of the polycyclic aromatic hydrocarbon (PAH) benz(a)anthracene (BA) near the sediment-water interface. In the absence of direct sunlight, degradation of ¹⁴C-labeled BA added to the water column was followed in the water column, in the sediment reservoir, and in the polychaete . Extensive metabolism of BA was observed in all components of the system.     

Ashes from fluidized bed combustion of residual forest biomass: recycling to soil as a viable management option

Although bottom ash (BA) [or mixtures of bottom and fly ash (FA)] from clean biomass fuels is currently used as liming agent, additive for compost, and fertilizer on agricultural and forest soils in certain European countries, in several other countries most of the ashes are currently disposed in landfills. This is due to both a lack of a proper classification of the materials and of regulatory barriers.Chemical characterization including analysis of an array of potentially toxic elements (PTEs) proved that over 100,000 tons of BA currently landfilled every year in Portugal actually complied with legal limits for PTEs for soil fertilizers applied in other countries. Pot experiments were conducted, testing three dosages of BA and FA (1, 2.5, and 5%, in weight) in three mining soils with different properties. Additions of ash materials to soils led to an increase in the pore water pH relative to control pots (0% of ash added) and had a clear impact on DOC and on the solubilization of both macro- and micronutrients (notably Cu).The results from the case study using BA and FA from a Portuguese biomass thermal power plant demonstrate that it is imperative to further develop a regulatory framework to alleviate technological and environmental barriers for biomass ash utilization as raw material for fertilizers and/or soil liming agent, in accordance with the goals of the circular economy. A more harmonized view on how to assess the merits and risks of the re-use of these materials is also needed.     

Hepatic and immune biological effect assays in C57BL/6 mice to measure polycyclic aromatic hydrocarbon bioavailability under laboratory exposures with increasing environmental relevance

Background Monitoring biological responses that are mediated via the aryl-hydrocarbon receptor (AhR) in animals exposed to environmental contaminants can indicate both the presence to chemicals that act through this biochemical pathway and whether these chemicals are bioavailable. Objectives The use of an ex-situ method that incorporated biological responsiveness monitoring in mice for determining the presence of ‘biologically active’ hydrocarbons in contaminated soils was investigated. Methods The use of C57BL/6 as a test organism was validated by determining hepatic and immune responsiveness to two polyaromatic hydrocarbons (PAHs): 3,4 benz[a]pyrene (B[a]P) and 1,2 benz (a)anthracene (BA) administered via intraperitoneal (i.p.) injection. The responsiveness of mice exposed to soils spiked with hydrocarbons or ex situ exposures to soil removed from two contaminated sites was also investigated. Results and Discussion Mice that were exposed to B[a]P via i.p. injections showed a 14-fold increase in liver microsomal ethoxyresorufin O-deethylase (EROD) activity compared to the control group. In contrast EROD activity following BA exposure at the same level was not significantly enhanced. Mouse immune response was significantly inhibited in a dose-dependent manner by i.p. injections of B[a]P. No significant inhibition occurred with the same doses of BA. Following i.p. exposure, the retention of B[a]P in mouse carcasses was greater than BA. Mice exposed to clean soils spiked with environmentally relevant concentrations of B[a]P and BA failed to show any significantly different hepatic or immune responses. Carcass residue data indicated a limited uptake of PAH from the soil. In contrast, EROD activity in mice exposed (ex situ) to hydrocarbon-contaminated soils removed from a fuel-loading depot and decommissioned gas works was significantly enhanced (4- and 2-fold respectively). However, this increase in EROD activity did not appear to correlate with either soil or carcass PAH concentrations. Conclusions and Outlook These results support the assumption that B[a]P has a higher affinity for the aryl hydrocarbon receptor (AhR) compared to BA. Soil parameters such as organic carbon content, structure and particle size distribution can modulate the bioavailability of contaminants to biological receptors. These factors are implicated in the lack of responsiveness demonstrated in the spiked soil experiments. However the responsiveness of EROD activity in mice exposed (ex situ) to soil contaminated with complex mixtures of hydrocarbon compounds confirms the potential usefulness of this model to determine the presence of ‘biologically active’ compounds in aged soils removed from contaminated sites.     

Distribution of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in municipal solid waste incinerators

The stack flue gases and the ashes in different units of two municipal solid waste incinerators (MSWIs) are sampled to investigate the characteristics of polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Bottom ashes (BA) exhibited much higher PBDD/F (8.11-52.2 pg TEQ/g) and PBDE contents (20.4-186 ng/g) than those of fly ashes (0.0932-2.02 pg TEQ/g and 0.332-25.5 ng/g), revealing that the PBDD/Fs and PBDEs in the feeding waste may not be completely destroyed. The PBDE concentrations/contents in the stack flue gases (26.1-109 ng/Nm³) and in the BA (20.4-186 ng/g) of the MSWIs could reach three orders higher than those in the atmosphere and reference soils. PBDE contributions to the environment from the stack flue gases or the reutilization of BA of MSWIs should not be ignored from the developing PBDE inventory.     

Wood pellet fly ash and bottom ash as an effective liming agent and nutrient source for rye grass (Lolium perenne L.) and oats (Avena sativa)

Fly ash (FA) and bottom ash (BA) from a softwood pellet boiler were characterized and evaluated as soil amendments. In a greenhouse study, two plant species (rye grass, Lolium perenne L. and oats, Avena sativa) were grown in three different treatments (1% FA, 1% BA, non-amended control) of a silty loam soil. Total concentrations of plant nutrients Ca, K, Mg, P and Zn in both ashes were elevated compared to conventional wood ash. Concentrations of Cd, Cr, Pb, Se and Zn were found to be elevated in the FA relative to BA and the non-amended soil. At 28 d, oat above-ground biomass was found to be significantly greater in soil amended with FA. Potassium and Mo plant tissue concentrations were significantly increased by addition of either ash, and FA significantly increased Zn tissue concentrations. Cadmium and Hg tissue concentrations were elevated in some cases. As soil amendments, either pellet ash is an effective liming agent and nutrient source, but high concentrations of Cd and Zn in FA may preclude its use as an agricultural soil amendment in some jurisdictions. Lower ash application rates than those used in this study (i.e. <1%) may still provide sufficient nutrients and effective neutralization of soil acidity.     

Assessment of a composting process for the treatment of beef cattle manure

The intensive breeding of beef cattle in Juncosa de les Garrigues (Catalonia, Spain) leads to the production of a large volume of manure that needs appropriate management. Land application in the area at agronomic rates is not enough to ensure good management practices, making necessary extended on-farm storage and the export of part of the production to long distances. In this context, the implementation of a collective treatment based on composting could help in enhancing the handling of manure. We assessed a full-scale composting process based on turned windrows (W), and involving treatment of beef cattle manure (CM) alone (two typologies were considered according to carbon-to-nitrogen ratios of ~25 (CM1, W1) and ~14 (CM2, W2)), or mixed with bulking agent (CM2/BA, W3) and dewatered digested sewage sludge (CM2/BA/DDSS, W4). Composting significantly improved the transportability of nutrients (final volumes were 40–54% of the initial volume). Temperature >55°C was reached in all the treatments but following different time patterns. Under the applied conditions of turning and rewetting, 14 weeks of processing did not ensure the production of stable, and mature, compost. Thus, only compost from W1 attained the maximum degree of stability as well as concentration of ammonium–N < 0.01% (with ammonium–N/nitrate–N ratio of 0.2) and low phytotoxicity. However, high pH, salinity, and heavy metal contents (Cu and Zn) may limit its final use. Addition of BA was advised to be kept to minimum, whereas use of DDSS as a co-substrate was not recommended in agreement to the higher loss of N and levels of heavy metals in the final compost.     

Composting of wastewater treatment sludge with different bulking agents

The main objectives of this study were to investigate the compostability of wastewater treatment sludge (WTS) containing different bulking agents (BAs) and to determine the most efficient BA. Four different compost trials consisting of mixtures of wheat straw (WS), plane leaf (PL), corncob (CC) and sunflower stalk (SS) with WTS were performed in laboratory reactors. In all experiments, a mixture of 60% WTS and 40% BA (wet basis) was used. The temperature, dry matter (DM), organic matter (OM), pH, electrical conductivity (EC) and C/N ratio were monitored during the composting process. Evaluation of the operational parameters showed that the highest organic matter degradation (i.e. 37.6%), loss of dry matter (i.e. 29.6%) and temperature (i.e. 64 °C) were achieved for the WTS-CC mixtures. Results also showed that the WTS-SS mixture was also successful in terms of these operational parameters. Use of bulking agents for the treatment of wastewater treatment sludge in composting process is an important issue with regards to process efficiency, economy and disposal of agricultural waste. Corncob and sunflower stalk that were previously not used for the composting of WTS from food industry were shown to be highly successful BA materials in this study.

Implications: The compostability of wastewater treatment sludge from the food industry with different bulking agents was studied. Wheat straw, plane leaf, corncob, and sunflower stalk were used as bulking agents. The required microbial stabilization and degree of mineralization were achieved with corncobs and sunflower stalks.     

Mercury in urban soils with various types of land use in Beijing, China

Mercury (Hg) concentration was investigated for 127 urban soil samples collected from business area (BA), classical garden (CG), culture and education area (CEA), public green space (PGS), residential area (RA) and roadside area (RSA) in Beijing. The median of Hg concentration in Beijing was 0.26 mg/kg. The value in CG was much higher than the other 5 types of land use, which was due to the historical use of Hg. More than 87% of the samples were not contaminated according to the guideline values of China, UK, Canada, and USEPA. Spatial distribution map revealed that Hg concentration showed a decreasing trend from the center to the suburb, it increased with the age of the urban area. Hg contamination in urban area of Beijing is marked by features of non-point sources associated with human activities, and it is most likely to be the common characteristics of Hg contamination in cities.     

Degradation of tert-butyl formate and its intermediates by an ozone/UV process

In this paper, the oxidation of tert-butyl formate (TBF) in aqueous solution by an ozone/UV process was described. The oxidation process was investigated experimentally in a semibatch reactor. The results of the study indicated that the ozone/UV process was very effective in oxidizing TBF. tert-Butyl alcohol (TBA), hydroxy-iso-butyraldehyde (HiBA), acetone, formaldehyde, and formic acid were identified as major primary intermediates during the oxidation of TBF. About 90% organic carbon balance was obtained indicating that most reaction intermediates have been identified and quantified. Some of the primary intermediates were also oxidized in the ozone/UV system. Accordingly, HiBA, acetone, formaldehyde, and formic acid were the primary intermediates of TBA oxidation. The oxidation of acetone in the ozone/UV system generated formaldehyde, pyruvaldehyde, acetic acid, formic acid as primary intermediates. It was also observed that the reaction intermediates formed during the oxidation of TBF react well in the ozone/UV system and complete mineralization could be achieved by the process.     

Degradation of tert-butyl formate and its intermediates by an ozone/UV process

In this paper, the oxidation of tert-butyl formate (TBF) in aqueous solution by an ozone/UV process was described. The oxidation process was investigated experimentally in a semibatch reactor. The results of the study indicated that the ozone/UV process was very effective in oxidizing TBF. tert-Butyl alcohol (TBA), hydroxy-iso-butyraldehyde (HiBA), acetone, formaldehyde, and formic acid were identified as major primary intermediates during the oxidation of TBF. About 90% organic carbon balance was obtained indicating that most reaction intermediates have been identified and quantified. Some of the primary intermediates were also oxidized in the ozone/UV system. Accordingly, HiBA, acetone, formaldehyde, and formic acid were the primary intermediates of TBA oxidation. The oxidation of acetone in the ozone/UV system generated formaldehyde, pyruvaldehyde, acetic acid, formic acid as primary intermediates. It was also observed that the reaction intermediates formed during the oxidation of TBF react well in the ozone/UV system and complete mineralization could be achieved by the process.     

Identification of a potential source of chloroform in urban air: Preliminary Communication

A new potential source of elevated chloroform (CHCl₃) concentrations in urban air is reported. The exhaust gases from gasoline internal combustion engines operated on conventional “leaded” fuel and not equipped with catalytic converters contain parts-per-billion concentrations of chloroform which can, in congested urban areas, contribute significantly to the ambient concentration of chloroform. Exhaust gases from engines burning conventional “leaded” gasoline contain much higher levels of chloroform than do exhaust gases from engines equipped with catalytic converters and operating on “nonleaded” gasoline.     

Environmental contamination of mercury from Hg-mining areas in Wuchuan, northeastern Guizhou, China

Total Hg and methyl-Hg were evaluated in mine wastes, soils, water, and vegetations from the Wuchuan Hg-mining areas, Guizhou, China. Mine wastes contain high total Hg concentrations, ranging from 79 to 710 microg g(-1), and methyl-Hg from 0.32 to 3.9 ng g(-1). Total Hg in soil samples range from 0.33 to 320 microg g(-1) and methyl-Hg from 0.69 to 20 ng g(-1). Vegetations present a high average total Hg concentration of 260 ng g(-1), which greatly exceeds the maximum Hg concentration of 20 ng g(-1) recommended by the Chinese National Standard Agency for food sources. The rice samples contain elevated methyl-Hg concentrations, ranging from 4.2 to 18 ng g(-1). Stream water collected from Hg-mining areas is also contaminated, containing Hg as high as 360 ng l(-1), and methyl-Hg reaches up to 5.7 ng l(-1). Data indicate heavy Hg-contaminations and significant conversion of methyl-Hg in the study areas.     

Joint action of ozone and hydrogen fluoride on foliar senescence in maize

Maize (Zea mays, L.) plants were exposed intermittently to O(3), HF or both pollutants and the progression of foliar senescence was followed by measuring chlorophyll loss, membrane breakdown and changes in stomatal conductance. At concentrations insufficient to cause foliar symptoms (0.06 microl O(3) litre(-1) and 1.0 microg Fm(-3)), exposures to HF had little or no effect, whereas O(3) exposures accelerated the rate of senescence. The rapid rate of senescence produced by O(3) was moderated if the plants were also exposed to HF. Topical application of 6-benzyladenine (BA) prior to pollutant exposures delayed senescence in all plants and completely prevented the O(3)-induced acceleration of senescence.     

Investigation of pathogenic Escherichia coli and microbial pathogens in pulp and paper mill biosolids.

Biosolids produced from pulp and paper mill wastewater treatment have excellent properties as soil conditioners, but often contain high levels of Escherichia coli. E. coli are commonly used as indicators of fecal contamination and health hazard; therefore, their presence in biosolids causes concern and has lead to restrictions in land-spreading. The objectives of this study were to determine the following: (1) if E. coli from the biosolids of a wastewater-free pulp and paper mill were enteric pathogens, and (2) if other waterborne microbial pathogens were present. E. coli were screened for heat-labile and heat-stable enterotoxin and verocytotoxin virulence genes using a polymerase chain reaction. Ten isolates were also screened for invasion-associated locus and invasion plasmid antigen H genes. None of the 120 isolates carried these genes. Tests for seven other microbial pathogens were negative. Effluents and biosolids from this mill do not contain common microbial pathogens and are unlikely to pose a health hazard.     

The use of Microtox to assess toxicity removal of industrial effluents from the industrial district of Camaçari (BA, Brazil)

The treatment efficiency, as toxicity removal, of complex effluents from the Industrial District of Cama?ari (BA, Brazil), after biological treatment with activated sludge was evaluated using Microtox. Samples of the equalised effluent (EE) were collected prior to treatment together with samples of the treated effluent (TE), which remained 24 h in the treatment plant. Rehydrated colonies of Vibrio fischeri were exposed to sequential dilutions of EE and TE to assess luminosity interference. Values for EC50 were calculated, together with the respective toxicity units. In all, twenty assays of each effluent type were carried out and the mean toxicity removal was 92.71%, while the chemical oxygen demand (COD) presented mean reduction of 83.04%. There was a variability of an order of magnitude between the Microtox results for the two types of effluents. The mean EC50 values were 2.12 for EE and 47.78% for TE. In spite of its weakness in some conditions, the Microtox system demonstrated to work adequately in assessing effluent toxicity removal in this treatment plant and therefore can be used for further toxicity removal programs.     

Nickel and other metal uptake and accumulation by species of Alyssum (Brassicaceae) from the ultramafics of Iran

Some plants growing on serpentine (ultramafic) soils are able to hyperaccumulate nickel in their above-ground parts. The genus Alyssum L. contains the greatest number of Ni-hyperaccumulator plants so far reported. There are substantial areas of serpentine soils at many locations in Iran. This paper presents the analyses for Ni, Cr, Mn, Fe, Mg and Ca in soils and Alyssum species from the ultramafics of west and northwest Iran. Soil analysis for total elements in these areas indicates that typical concentrations of Ni, Cr, Mn, Fe, Mg and Ca are up to about 1240, 365, 800, 51,150, 152,390 and 11,790 microg g(-1), respectively. During this study, seven Alyssum species were collected. Analysis of leaf dry matter shows that Alyssum bracteatum can contain up to 2300 microg Nig(-1), while the other species contain much lower concentrations of Ni and other elements. A. bracteatum is endemic to Iran and the first Ni hyperaccumulator reported from this species.     

A sensitive enzyme‐linked immunosorbent assay amplified by biotin–streptavidin system for detecting non‐steroidal anti‐inflammatory drug ketoprofen

A sensitive biotin–streptavidin‐amplified enzyme‐linked immunosorbent assay (BA‐ELISA) method was developed for detecting non‐steroidal anti‐inflammatory drug ketoprofen. Compared with traditional ELISA method, the sensitivity of proposed immunoassay was enhanced by the biotin–streptavidin system. Under the optimal condition, the median inhibitory concentration (IC₅₀) was 0.25 ng mL^?1, with minor cross‐reactivity to a number of structural analogs. This developed assay was successfully applied to detect the ketoprofen residues in different fish samples, and good recoveries (72.6–105.5%) were obtained. The results indicated that this immunoassay method could specifically detect trace ketoprofen residues and could be widely used for routine monitoring of food samples.