Green Biomass Materials in Polyurethane Foams

Flexible polyurethane foams were prepared using naturally derived materials as alternatives to conventional auxiliary blowing agents. This research was based on the concept held by some that natural chemicals are better as a part of industrial ecology. The authors have attempted to define the foam manufacturing suitability of natural chemicals, but have not defined or defended the policy implications of such choices. Natural chemicals are often less suitable than those refined from petroleum and may then need some environmental credit related to greater discharge to be viable substitutes. Modest decreases in density (relative to foams without any auxiliary blowing agent) were obtained with the addition of solid CO₂ but other physical properties were not measured. It is unclear whether the reduction in density is a result of the phase change of CO, from solid to liquid within the polyurethane cell matrix or simply a bubbling effect of C02 in solution causing voids within the final product. Although it was anticipated that the high boiling point of limonene, from citrus peeis, would negate effectiveness as an auxiliary blowing agent, there were analogous decreases in foam density. The observed effect might be rationalized by the significant vapor pressure of limonene at temperatures lower than the boiling point. The limonene may be sweptf rom the foam system coincident with the loss of in situ generated CO₂ isoprene, naturally emitted from deciduous vegetation as well as from the combustion of carbonaceous fuels, provides a useful, if not complete, range of foam densities and may then be a partial substitute for halogenated auxiliary blowing agents. Switching from methyiene chloride to isoprene as the auxiliary blowing agent of choice would immediately decrease organic emissions from polyurethane foam plants by 20 percent (molecular weight effect). Regulation as a VOC and the residual acrid odor may be potential drawbacks to commercial utilization of isoprene.     

Historic emissions of fluorotrichloromethane (CFC-11) based on a market survey

Releases of CFCs occur promptly from applications such as aerosol sprays, or over a period of several years from refrigeration and air conditioning or more slowly still from use as blowing agents for closed cell plastic foams. As a consequence of the Montreal Protocol, the emissions have fallen and their pattern is continuing to change. To help quantify these changes the emissions from closed cell foam blowing have been re-examined in a comprehensive market survey, developing a lifecycle assessment for each foam type, production method and foaming agent.The original model for the time series of emissions from foam applications was shown to remain a robust representation in general terms. There is an “immediate” loss when the foam is manufactured, a slow emission from the foam itself during use and a loss on disposal of the artefact made with the foam. The original model used an initial loss rate of 10% and a subsequent loss of 4.5% yr⁻¹ over 20 yr.The new survey showed a wide range of initial and service loss rates. Immediate release ranges from 95% down to 4%; similarly, the rate of loss during service varies from 0.5% to 5% yr⁻¹ and the service lifetimes of the artefacts made with the foams varies from 12 to 50 yr. The apparent emission function, in terms of the mean value of the annual fractional release from the bank of CFC-11 residing in foams, was calculated from the survey to be 0.043±0.008 over 28 yr. There is a small and non-significant fall in this function with time; so that over the last ten years of the data record the more appropriate value is 0.0366±0.0008. However, up to the early 1990s, it is the original emission function that is consistent with the observed atmospheric concentrations. Thenceforth this function seriously overpredicts the concentrations but, if the new emissions function for foams is used from 1993 onwards in conjunction with the original emission functions for all other uses, the fit becomes better. This suggests that the emission functions for prompt and short term releases remain valid and should be coupled with the new function to calculate emissions of CFC-11 or other fluorocarbon foam blowing agents from the early 1990s onwards.     

A Qualitative Analysis of the Effects of Water Vapor on Multi-Component Vapor-Phase Carbon Adsorption

The effects of water vapor on binary vapor adsorption of toluene and methylene chloride by activated carbon were investigated on a bench-scale experimental system. Three levels of relative humidity (15, 65 and 90 percent) in conjunction with different concentrations of individual adsorbates (from 400 to 1200 ppmv) were tested by tracing the breakthrough curves of each adsorbate eluted from a fixed-bed adsorber. The adsorption capacities of the activated carbon tested for each adsorbate under the various conditions were obtained from calculations based on area integration of the breakthrough curves. It was found that with increasing relative humidity, the shape of breakthrough curves was asymmetrically distorted and the width of the breakthrough curves was broadened for toluene and steepened for methylene chloride. The adsorption capacities for both toluene and methylene chloride were decreased with the increase of relative humidity. The magnitude of the effect of water vapor is greater at the lower toluene concentration and at the higher concentration of methylene chloride. The mechanisms of water vapor influence on the process of multicomponent vapor adsorption are discussed.     

高稳定性污泥蛋白发泡剂的发泡特性及应用研究

以污泥蛋白为实验材料,通过加入不同量的稳定剂GP-1,配制成高稳定性污泥蛋白发泡剂,并对高稳定性污泥蛋白发泡剂的发泡特性和影响因素进行研究。结果表明,以污泥蛋白10 mL、水90 mL、GP-1 0.4 g配方组合为研究对象,所制备的泡沫初始体积为770 mL,泡沫泌水时间大于15 h,泡沫半衰期大于64 h,泡沫综合发泡能力为2.2×10⁶ mL·min,泡沫的最佳搅拌时间为5 min,泡沫的泌水时间和泡沫的半衰期都是随着温度的上升而下降,在pH为3～13时泡沫稳定。经过对高稳定性污泥蛋白发泡剂发泡特性研究以及对水泥的胶凝时间、特性进行比较,研制出污泥蛋白泡沫混凝土发泡剂,并制备污泥蛋白泡沫混凝土块;结果表明,当污泥蛋白泡沫混凝土发泡剂的用量分别为0、6、6.8、7.6、8.4和9.2 mL,水泥为200 g时,制备泡沫混凝土块,其密度由2.07 g/cm³下降到0.34 g/cm³,体积由130 cm³ 上升到755 cm³;在泡沫混凝土块脱模后的第1 d、第7 d、第28 d分别称量他们的重量变化情况,结果表明,泡沫混凝土块第1 d和第7 d无重量变化,第28 d的重量明显减轻。该研究为污泥蛋白研制成为泡沫混凝土发泡剂,并应用于屋面隔热、保温建立前期基础。     

A Thermal Desorption Procedure for Determining Residual Blowing Agent (CFC-11) in Rigid Foam

A method for measuring the cell gas content in rigid foams has been developed. A unique foam extraction device and a thermal desorption system were developed to expedite gas extraction and analysis. CFC-11 found by this method was in excellent agreement with the calculated value in a commercially formulated foam (7.1 versus 7.8 percent). Average method precision (i.e., relative standard deviation) from processing nine foam samples (in duplicate) was 1.9 percent. The method has also been successfully applied to foams containing non-GFC blowing agents.     

Gasoline Evaporation–Ethanol and Nonethanol Blends

Tests were performed to compare the evaporation rate of 10 volume percent (vol%) ethanol-blended gasoline (E10) with the evaporation rate of its base gasoline. Weight loss, temperature, pressure, and humidity were monitored as lab-blended E10 and base gasolines were evaporated concurrently from glass cylinders placed on balances located side by side under an exhaust hood. The averaged results of four tests at about 70°F showed that the E10 lost more total weight to evaporation than the base fuel, but less gasoline. The increased weight was due to ethanol, which was present in the E10 evaporative emissions at concentrations of about 13 weight percent (wt%). In two-hour tests at temperatures near 70°F, during which 4.5 to 5.3 wt% of initial fuel samples were evaporated, E10 fuels lost an average of about 5% less gasoline than their base fuels. A similar result was obtained for a one-hour test, during which about 2.4 to 2.5 wt% of the initial fuel samples were evaporated. Gas chromatography (GC) component analysis indicated that the compositions of the ethanol-free emissions from the two fuels were similar. Reid vapor pressure (RVP) measurements made using a Grabner CCA-VPS according to ASTM D5191-91 indicated that E10 fuels underwent an approximate 5% greater RVP reduction than their respective base fuels.     

Evaluation of alternative filter media for particulate matter emission testing of residential wood heating devices

The performance of Teflon-coated glass fiber filter media (Pallflex Emfab TX40) is evaluated for particulate matter (PM) sampling of residential wood heating devices in a dilution tunnel. Thirty samples of varying duration and PM loading and concentration were collected from an U.S. Environmental Protection Agency (EPA) Method 28 dilution tunnel using dual Method 5G sample trains with untreated glass fiber and Emfab filters. Filters were weighed soon after the end of sampling and again the next day after equilibration at 35% relative humidity (RH). PM concentrations from both types of filters agreed very well with 1-day equilibration, demonstrating that Emfab filters are appropriate for use in measuring PM from residential wood burning appliances in a dilution tunnel and have performance equal to or better than the glass fiber filter media. Agreement between filter media without equilibration was erratic, with PM from glass fiber filter samples varying from slightly less than the Emfab samples to as much as 2.8 times higher. Some of the glass fiber filters lost substantial mass with equilibration, with the highest percent loss at lower filter mass loadings. Mass loss for Emfab samples was a small percentage of the mass and very consistent across the range of mass loadings. Taken together, these results may indicate water uptake on the glass fiber media that is readily removed with 1-day equilibration at moderate RH conditions.

Implications: EPA regulations now allow the use of either glass fiber or Teflon filter media for wood appliance PM emission testing. Teflon filter media minimizes the potential for acid-gas PM artifacts on glass fiber filters; this is important as EPA moves toward the use of locally sourced cordwood for testing that may have higher sulfur content. This work demonstrates that the use of Teflon-coated glass fiber filters can give similar PM measurement results to glass fiber filters after 1 day of equilibration. With no equilibration, measured PM from glass fiber filters was usually higher than from Teflon-coated glass fiber filters.     

Determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine with mass selective detection.

Method development and validation studies have been completed on an assay that will allow the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. The accurate determination of 2,4-D in urine is an important factor in monitoring worker and population exposure. These studies successfully validated a method for the detection of 2,4-D in urine at a limit of quantitation (LOQ) of 5.00 ppb (parts per billion) using gas chromatography with mass selective detection (GC/MSD). The first study involved the determination of 2,4-D in control human urine and urine samples fortified with 2,4-D. Due to chromatographic interference, a second study was conducted using 14C-2,4-D to verify the recoverability of 2,4-D from human urine at low levels using the GC/MSD method. The second study supports the results of the original data. The 2,4-D was extracted from human urine using a procedure involving hydrolysis using potassium hydroxide, followed by a liquid-liquid extraction into methylene chloride. The extracted samples were derivatized with diazomethane. The methylated fraction was analyzed by GC/MSD. Quantitation was made by comparison to methylated reference standards of 2,4-D. Aliquots fortified at 5-, 50-, and 500-ppb levels were analyzed. The overall mean recovery for all fortified samples was 90.3% with a relative standard deviation of 14.31%.     

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.     

Road deicing salt irreversibly disrupts osmoregulation of salamander egg clutches

It has been postulated that road deicing salts are sufficiently diluted by spring rains to ameliorate any physiological impacts to amphibians breeding in wetlands near roads. We tested this conjecture by exposing clutches of the spotted salamander (Ambystoma maculatum) to three chloride concentrations (1 mg/L, 145 mg/L, 945 mg/L) for nine days, then transferred clutches to control water for nine days, and measured change in mass at three-day intervals. We measured mass change because water uptake by clutches reduces risks to embryos associated with freezing, predation, and disease. Clutches in controls sequestered water asymptotically. Those in the moderate concentrations lost 18% mass initially and regained 14% after transfer to control water. Clutches in high concentration lost 33% mass and then lost an additional 8% after transfer. Our results suggest that spring rains do not ameliorate the effects of deicing salts in wetlands with extremely high chloride concentrations.     

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.     

Potential role of fire retardant-treated polyurethane foam as a source of brominated diphenyl ethers to the US environment

Five tetra- to hexabrominated diphenyl ether (BDE) congeners (BDE-47, -99, -100, -153 and -154) are the most frequently reported in wildlife and humans. The commercial penta-BDE product, used predominantly to flame-retard polyurethane foam, consists primarily of these same congeners. In 1999, North American demand accounted for 98% of the total global penta-market of 8500 metric tons. Frogs, housed with flame retardant-treated polyurethane foam as a dry substrate, accumulated 10,100 microg/kg (wet weight) of the above BDEs. Crickets kept therein as food contained 14,400 microg/kg. The crickets are believed to have browsed directly on the foam and, in turn, were consumed by the frogs. BDE congener composition in all three matrices matched that of the penta-commercial product. Similar congeners were also observed in soil and stream sediments collected near a polyurethane foam manufacturing plant. Summed concentrations of BDE-47, -99 and -100, the dominant congeners observed in these samples, ranged from < 1 to 132 microg/kg (dry weight basis). Sunfish fillets obtained from a nearby, off-site pond contained a total of 624 microg/kg (lipid basis). Sewage treatment plant (STP) sludge exhibited these same congeners at 1370 microg/kg (dry weight). BDE-209, the fully brominated congener predominant in the commercial deca-BDE product, was also present at 1470 microg/kg. While no known polyurethane foam manufacturers discharged to this plant, the distribution pattern of the low brominated congeners in the sludge matched that of the penta-product. After four weeks of exposure to ambient outdoor conditions, the surface of flame-retarded polyurethane foam became brittle and began to disintegrate. Subsequent dispersal of these penta-containing foam fragments may be one mechanism by which these BDEs reach the environment.     

Reductive dechlorination of chlorinated methanes and ethanes by reduced iron (II) porphyrins

The reaction of a reduced iron (II) porphyrin with a series of chlorinated methanes and ethanes was examined under neutral conditions in buffered aqueous solutions containing an excess of the reducing agent. Carbon tetrachloride, chloroform and 1,1,1-trichloroethane were reduced to lower chlorinated homologs, while methylene chloride, 1,1,2-trichloroethane and 1,1-dichloroethane did not appear to be degraded in this system.     

Polyurethane foam (PUF) disks passive air samplers: wind effect on sampling rates

Different passive sampler housings were evaluated for their wind dampening ability and how this might translate to variability in sampler uptake rates. Polyurethane foam (PUF) disk samplers were used as the sampling medium and were exposed to a PCB-contaminated atmosphere in a wind tunnel. The effect of outside wind speed on PUF disk sampling rates was evaluated by exposing polyurethane foam (PUF) disks to a PCB-contaminated air stream in a wind tunnel over air velocities in the range 0 to 1.75 m s-1. PUF disk sampling rates increased gradually over the range 0-0.9 m s-1 at approximately 4.5-14.6 m3 d-1 and then increased sharply to approximately 42 m3 d-1 at approximately 1.75 m s-1 (sum of PCBs). The results indicate that for most field deployments the conventional 'flying saucer' housing adequately dampens the wind effect and will yield approximately time-weighted air concentrations.     

玉米深加工废水的混凝实验

在室温条件下,分别选用聚合氯化铝(PAC)、聚合氯化铝铁(PAFC)及三氯化铁(FeCl3)对玉米深加工废水进行混凝实验。综合考虑各种混凝剂对磷、COD以及SS的去除效果,最终选取PAC作为混凝剂。采用PAC和聚丙烯酰胺(PAM)作为复合混凝剂,对其去除效果做进一步研究,并确定了最佳投加量及pH值。实验结果表明,在PAC投加量25mg/L,PAM投加量0.5 mg/L,pH为8条件下,混凝效果最佳。磷、COD、SS去除率可分别达到90.1%、53.3%和88.2%,对应的出水质量浓度分别为0.41、26.8和2 mg/L。     

Foam Fractionation of Black Liquor From Sulfate Pulping

The principal deterrent of general acceptance of weak black liquor oxidation by mills pulping southern pine is the extensive foam produced during the oxidation of the liquor. The foam results from relatively high concentrations of fatty and rosin acid soaps remaining in the black liquor after roughly 75% of these compounds have been removed by skimming as marketable by-products. The foaming propensity of black liquor can be used to advantage to provide additional by-product recovery while the black liquor is being oxidized. This paper will report the results of foam fractionation studies on such black liquors conducted in this laboratory.     

The Removal of Particulate Matter from Fluid Bed Catalytic Cracking Unit Stack Gases

The application of a high-efficiency centrifugal type of separator to fluid bed catalytic cracking units is described in which most of the catalyst particles often lost to the atmosphere are concentrated into a small part of the stack gas (2%). A further separation can then be made on this small stream by an auxiliary separator which further concentrates the catalyst particle into 0.1% of the initia stream. Performance of the main and auxiliary separators are such as to reduce the loss of catalyst particles in the stack gas from 800 ppm to less than 60 ppm in a typical unit. Large amounts of power can be recovered by application of expander turbines to catalytic cracking plants employing this system of separation.     

A net water production model for ultrafiltration including flow direction reversal and chemically assisted backwashing.

Flow direction reversal (FDR) was proposed as a novel method to increase net water production (NWP) during cross-flow ultrafiltration. The design of the pilot-plant study allowed measurement of specific flux recovery after each chemically assisted backwash (BW) combined with FDR and after each FDR at the midpoint of each BW/FDR cycle. The percent recovery of specific flux was higher following FDR (55%) than combined BW and FDR (53%) at lower chemical dosages; however, the percent increase in specific flux recovery by FDR was much lower (20%) when the chemical dose was doubled. A mathematical model was developed to predict the NWP achieved by any combination ofBW/ FDR and FDR frequency. For example, the advantage of introducing FDR was demonstrated at the lower chlorine dose, whereby the percent increase in NWP by alternating 15-minute intervals of BW/FDR with FDR over BW/ FDR alone was 10% for 30-minute BW/FDR intervals and 2% for 15-minute BW/FDR intervals.     

Inhalation exposure to volatile organic compounds in the printing industry

ABSTRACT

This study reports on the occupational inhalation exposure to VOCs of workers in the Kuwaiti printing industry. Using the evacuated canister methodology, we targeted 72 VOCs in three printeries and compared the concentrations to previous reports and relevant occupational exposure levels (OELs). We found that recent efforts in the printing industry to reduce VOC usage had been successful, as concentrations of key hazardous VOCs were substantially lower than anticipated. On the other hand, nearly all target VOCs were found. Non-production areas were sampled along with the offset printing areas, another strength of this study, and revealed exposures to hazardous VOCs among administers and digital printer and CTP operators. Exposure to ototoxic VOCs amounted to 1–3% of the OEL, consisting mostly of ethylbenzene, which was likely in use in two of the study printeries. Exposure to carcinogenic or probably carcinogenic VOCs was 15–20% of the OEL at four locations across the three printeries, consisting mostly of vinyl chloride and benzyl chloride. Vinyl chloride VOC was partially sourced from outdoors, but was also likely used inside the study printeries. Interestingly, concentrations of vinyl chloride were similar in most sampling locations to that of CFC-114, a CFC banned by the Montreal Protocol and not commonly used as a refrigerant. This unexpected finding suggests further study is warranted to identify the use of these VOCs in printeries. Exposure to hazardous VOCs up to nearly 50% of the OEL, consisting largely of bromoform and vinyl chloride. Bromoform was found in all the study printeries, sourced partially from outdoor air. The higher concentrations found inside the study printeries likely resulted from the use of the desalinated water for washing. This finding raises of emissions from sources other than blanket washes, and inks, etc. adding to the total VOC load in printery indoor air.

Implications: Results from this study indicate that efforts to reduce worker exposure to VOCs particularly dangerous to human health in recent years have been successful, but there is still much to be done to protect workers. Exposures to ototoxic and carcinogenic VOCs were identified, among both production and non-production workers. Unexpected findings included the apparent use in printing activities of the carcinogen vinyl chloride and CFC-114, banned under the Montreal Protocol. Observed lapses in safety procedures included failure to utilize ventilation systems and closing doors between work areas, indicating management and worker education should remain a priority.     

Effect of airborne bromoxynil-octanoate and metribuzin on non-target plants

The present study was conducted to determine the effects of airborne herbicides on the photosynthesis and growth of non-target plants. Sunflowers at different growth stages were used as test plants and exposed for 24 h in a wind tunnel to a range of concentrations of bromoxynil-octanoate and metribuzin. The quantum yield (phiPSII) and the dry weight were used as response parameters. Results indicate that young sunflower plants are affected by sublethal concentrations of both herbicides, whereas metribuzin proved to be more phytotoxic. Bromoxynil-octanoate and metribuzin concentrations > 0.265 and >0.135 microg/m(3) impair the photosynthetic activity of exposed leaves and concentrations >0.780 and >0.641 microg/m(3) of leaves developed after exposure. Effects on dry weight indicate that younger plants were more susceptible, whereby the response to metribuzin proved to be more dependent on growth stage. Based on these results and considering herbicide concentrations in ambient air, there is a reasonable probability that non-target plants are temporarily at risk of being affected.