[Simultaneous determination of three organic fluorides in workplace air by portable gas chromatography-mass spectrometer].

OBJECTIVE: To establish a method for rapid determination of organic fluorides in the air of a fluorine chemical plant using portable gas chromatography-mass spectrometer (GC-MS). METHODS: Standard samples of monochlorodifluoromethane, tetrafluoroethylene, and hexafluoropropylene of different concentrations were prepared by static volumetric method with high-purity nitrogen as the diluent gas. The samples were injected into the GC-MS by a hand-held probe. Retention time and characteristic ion were used for qualitative analysis, and the area of selected ion peak was used for quantitative analysis. The standard curves were then created for quantitative determination of the three organic fluorides. RESULTS: The linear ranges for monochlorodifluoromethane, tetrafluoroethylene, and hexafluoropropylene by the method were 0.39-7.72, 0.45-8.84, and 0.61-12.20 mg/m3, respectively, the average recovery rates for the three concentrations were 102.8%, 96.0%, and 106.5%, respectively, and the average deviations were 2.1%, 5.1%, and 2.4%, respectively. CONCLUSION: The portable GC-MS can be used for the simultaneous qualitative and quantitative analysis of monochlorodifluoromethane, tetrafluoroethylene, and hexafluoropropylene in the workplace air, and the method is simple, fast, and accurate.

Multiannual top-down estimate of HFC-23 emissions in East Asia.

Trifluoromethane (CHF3, HFC-23), with a 100-year global warming potential (GWP) of 12400, is regulated under the Kyoto Protocol. HFC-23 emissions in East Asia, especially in China, are currently thought to represent the majority of global HFC-23 emissions. This study provides both a bottom-up emission inventory and the multiannual top-down estimate of HFC-23 emissions in East Asia during 2007-2012. The new bottom-up inventory yields improved simulated HFC-23 mixing ratios compared to previous bottom-up inventories. The top-down estimate uses inverse modeling to further improve the model-measurement agreement. Results show that China contributed 94-98% of all HFC-23 emissions in East Asia. Annual a posteriori emissions from China were around 6.3 Gg/yr during the period 2007-2010 after which they increased to 7.1 ± 0.7 Gg/yr in 2011 and 8.8 ± 0.8 Gg/yr in 2012. For the first time, this study also provides a top-down estimate of HFC-23/HCFC-22 (chlorodifluoromethane, CHClF2) coproduction ratios in non-CDM (Clean Development Mechanism) HCFC-22 production plants as well as in all HCFC-22 production plants in China.

Effects of acoustic hood on noise, CFC-11, and particulate matter in a recycling system for waste refrigerator cabinet.

The mechanical-physical process was proven to be technologically feasible for waste refrigerator recycling and has been widely used in the typical e-waste recycling factories in China. In this study, effects of the acoustic hood on the reduction of noise level, CFC-11, and heavy metals (Cr, Ni, Cu, Cd, and Pb) in particulate matter (PM) were evaluated. For noise pollution, the noise level inside and outside the acoustic hood was 96.4 and 78.9 dB, respectively. Meanwhile, it had a significant effect on A-weighted sound level with a reduction from 98.3 to 63.6 dB. For CFC-11 exposure, abundant CFC-11 (255 mg/m(3)) was detected in the acoustic hood. However, the mean concentration of CFC-11 at the outline of polyurethane foam collection was obviously diminished to 14 mg/m(3), and no CFC-11 was monitored around the acoustic hood. The concentrations of PM and heavy metals in PM outside the acoustic hood were lower than those inside the acoustic hood due to the physical barriers of the acoustic hood. Based on the risk assessment, only adverse health effect caused by Pb might likely appear. All the results can provide the basic data for pollution control and risk assessment in waste refrigerator recycling system.

Historical emissions of HFC-23 (CHF3) in China and projections upon policy options by 2050.

Trifluoromethane (CHF3, HFC-23) is one of the hydrofluorocarbons (HFCs) regulated under the Kyoto Protocol with a global warming potential (GWP) of 14 800 (100-year). China's past, present, and future HFC-23 emissions are of considerable interest to researchers and policymakers involved in climate change. In this study, we compiled a comprehensive historical inventory (1980-2012) and a projection (2013-2050) of HFC-23 production, abatements, and emissions in China. Results show that HFC-23 production in China increased from 0.08 ± 0.05 Gg/yr in 1980 to 15.4 ± 2.1 Gg/yr (228 ± 31 Tg/yr CO2-eq) in 2012, while actual HFC-23 emissions reached a peak of 10.5 ± 1.8 Gg/yr (155 ± 27 Tg/y CO2-eq) in 2006, and decreased to a minimum of 7.3 ± 1.3 Gg/yr (108 ± 19 Tg/yr CO2-eq) in 2008 and 2009. Under the examined business-as-usual (BAU) scenario, the cumulative emissions of HFC-23 in China over the period 2013-2050 are projected to be 609 Gg (9015 Tg CO2-eq which approximates China's 2012 CO2 emissions). Currently, China's annual HFC-23 emissions are much higher than those from the developed countries, while it is estimated that by year 2027, China's historic contribution to the global atmospheric burden of HFC-23 will have surpassed that of the developed nations under the BAU scenario.

Prediction of future disposal of end-of-life refrigerators containing CFC-11.

The objective of this study was to predict the number of refrigerators containing CFC-11 blown isolation foam and the amount of CFC-11 banked in these refrigerators. By using a Weibull-based survival function, the number of CFC-11 containing and still-functioning refrigerators was estimated to be approximately 1.6 million in 2013 in Turkey. In order to determine the amount of CFC-11 in the isolation foam of these refrigerators, polyurethane (PU) foam samples were taken from a refrigerator manufactured in 1993 and the quantity of CFC-11 was analyzed by a GC-MS. It was determined that 113-195 mg CFC-11/g PU remains in the PU foam depending on the location such as door, sides, top and bottom. Knowing that a mid-sized refrigerator contains 4 kg PU on average, the total amount of PU foam to be disposed of is 6344 tons when the CFC-11 containing refrigerators in Turkey become obsolete in the near future. Furthermore, 717-1237 tons of CFC-11 are expected to be banked in the PU foam of these refrigerators which will exert an equivalent amount of ozone depleting potential (ODP). In addition, the global warming potential will vary between 3.4 and 5.9 million tons of CO2.

The use of a custom mode electron capture detector to determine mixing ratios of environmental tracers: Sulfur hexafluoride, chlorotrifluoromethane and bromotrifluoromethane.

Atmospheric concentrations of anthropogenic trace gases, such as sulfur hexafluoride, SF6, chlorotrifluoromethane, CF3Cl, and bromotrifluoromethane, CF3Br, are increasing. Their long lifetimes and limited chemical reactivity make them attractive environmental tracers for hydrology and oceanography. While ambient SF6 concentrations can be readily measured using GC-ECD, the simultaneous analysis of CF3Cl and CF3Br is hampered due to their low ECD sensitivity. The response of a commercial ECD for those gases was enhanced using the resonance detection mode which is based on shifting the mean energy of electrons in the ECD detector towards the region where the electron-capture reaction reveals a distinct maximum. A custom electronic system enabled operation of a commercial ECD in the resonance detection mode. An approximately 50-fold amplification of the ECD signal was obtained for CF3Cl by application of high-frequency electric field (amplitude of 50V and frequency of 40MHz). For CF3Br, a 3.5-fold increase of the ECD signal was obtained, with a lower HF field (20-30V). In the case of SF6 the application of the HF field reduces the magnitude of ECD signal by a factor of 40. The electron-capture coefficients for SF6, CF3Cl and CF3Br were determined from 453 to 633K in the standard and the resonance modes. The electron-capture coefficients for CF3Cl and CF3Br increase with increasing temperature for both modes, while that for SF6 decreases slightly with increasing temperature. The application of the resonance detection mode to a commercial ECD provides an attractive and cost-effective alternative to GCMS for high-quality quantitative analyses of CF3Cl and CF3Br as environmental tracers.

Risks in the physical recovery system of waste refrigerator cabinets and the controlling measure.

Environmental information in physical recovery system of waste refrigerator cabinets was provided in this paper. The system included closed shearing, activated carbon adsorption (ACA), air current separation, magnetic separation, and eddy current separation. Exposures of CFC-11, heavy metals, and noise emitted from the system were assessed. Abundant CFC-11 (>510 mg/m³) was detected in crusher cavity. However, due to the employment of ACA, little CFC-11 (<9.5 mg/m³) could be detected out the recovery system. Heavy metals were detected in the air of workshop (TSP: Cu ≤ 4.91 µg/m³, Pb ≤ 3.17 µg/m³, PM10: Cu ≤ 2.1 µg/m³, Pb ≤ 1.3 µg/m³). Assessment results indicated the concentrations of heavy metals in air were safe for workers. Copper (25.8 mg/kg) and lead (19.5 mg/kg) were found in ground dust of the workshop and the concentrations were safe for soils. Noise level (98.2 dB(A)) of crushing process could cause disease and hearing impairment to workers. For controlling noise, acoustic hood was designed to reduce the noise level to 69.7 dB(A).The above information was of assistance to the industrialization of physical process for recovering waste refrigerator cabinets on environmental protection. Meanwhile, it contributed to the knowledge of environmental information of physical technology for recovering e-waste.

How to improve reliability in groundwater analysis: over a decade of experience with external quality control in field campaigns on volatile halogenated compounds.

The reliability in measurement results obtained during environmental monitoring is crucial for the assessment and further planning of remediation efforts on the respective contaminated sites by the responsible authorities. A case study concerned with groundwater contaminated with perchloroethylene, trichloroethylene and 1,1,2-trichlorotrifluoroethane including their degradation products which involves private contract laboratories and an independent provider of quality assurance (QA) is presented. The experience gained with biannual monitoring campaigns over 14 years indicates that the selection of contractors on basis of accreditation status and successful performance in interlaboratory comparisons are not sufficient. Rather the auditing of the contractors by the QA provider prior to each campaign and the crosschecking of selected monitoring samples by the QA provider led to a lasting improvement of reliability in the contractors' measurement results. A mean deviation of 20% from the reference value determined by the QA provider for the crosschecked samples was reached.

The application of "in-flight" laser diffraction to the particle size characterization of a model suspension metered dose inhaler.

Laser diffraction (LD) has been used to measure the particle size of pharmaceutical aerosols. In this study, the application of LD for measuring the particle size of a model suspension metered dose inhaler (MDI) containing a hydrofluorocarbon propellant was investigated using a Sympatec LD apparatus with an automatic spray device. In order to obtain meaningful results, test parameters such as spray distance and temperature needed to be optimized for this model formulation and then well-controlled during testing. Using a suitable LD test methodology, it was found that particle size variations as a function of nonvolatile excipient levels as well as changes to the suspended drug substance could be observed and, in some cases, correlated to cascade impaction results. Based on these studies, it is believed that the methodology is a valuable rapid screening tool for investigating variations in or permutations to suspension MDI formulations. Nonetheless, the trends in the LD droplet size are complicated by the presence of drug-free droplets. Consequently, the results are not always consistent with other particle sizing techniques such as cascade impaction in which the droplets associated with drug are evaluated. Therefore, for suspension MDIs, the "in-flight" LD method would probably best be utilized as a complementary sizing technique during formulation development.

[In situ measurement of atmospheric HCFC-22 at the Shangdianzi GAW regional station].

An in situ GC-ECD monitoring system was established at the Shangdianzi GAW Regional station from April 2007 to March 2008, and the mixing ratio of atmospheric HCFC-22 was (278.1 +/- 113.6) x 10(-12) (mol/mol). A "R" statistical software was applied to the HCFC-22 time series to separate background and pollution data. The background HCFC-22 mixing ratio was (199.5 +/- 5.1) x 10(-12), close to northern hemisphere background level observed at Mace Head and Trinidad Head stations. The pollution HCFC-22 mixing ratio was (312.1 +/- 121.0) x 10(-12) due to anthropogenic emission from various regions and air mass transport. There was no significant seasonal variability of background data. However, pollution data was much higher in summer than that in winter, and elevated up to 100.9 x 10(-12) in July than in January attribute to seasonal emission characteristics. The mean HCFC-22 mixing ratio from southwest wind sector (327.3 x 10(-12)) was much higher than that of northeast sector (236.2 x 10(-12)). The W-WSW-SW wind sector has a positive contribution to the HCFC-22 level, while NNE-N-NE has a large negative contribution.

Carbon dioxide emission implications if hydrofluorocarbons are regulated: a refrigeration case study.

The U.S. is strongly considering regulating hydrofluorocarbons (HFCs) due to their global climate change forcing effects. A drop-in replacement hydrofluoroether has been evaluated using a gate-to-grave life cycle assessment of greenhouse gas emissions for the trade-offs between direct and indirect carbon dioxide equivalent emissions compared to a current HFC and a historically used refrigerant. The results indicate current regulations being considered may increase global climate change.

Simultaneous analysis of atmospheric halocarbons and non-methane hydrocarbons using two-dimensional gas chromatography.

A gas chromatographic system was constructed to simultaneously measure ambient non-methane hydrocarbons (NMHCs) and halocarbons, which play significant roles in tropospheric ozone formation and stratospheric ozone loss, respectively. A heart-cut device based on a Deans switch was connected to two capillary columns to cover the full range of NMHCs and halocarbons. Analytes more volatile than C(6) NMHCs and the halocarbon CFC-113 were separated with a PLOT column, while the remaining less volatile compounds were separated with a DB-1 column. Merge-and-split of the flows at the end of the two columns allowed the NMHCs and halocarbons to be observed simultaneously by electron capture detection (ECD) and flame ionization detection (FID). To avoid peak-overlap from the two columns while merging, programmed pressures were incorporated to control the Deans switch. In addition to the advantage of measuring two important classes of compounds in the atmosphere at the same time, this method has the additional benefit of using the homogeneity of atmospheric CFC-113 as an "intrinsic" internal reference. Thus, better data continuity, less consumption of gas standards, and real-time quality control can all be achieved.

Simultaneous determination of CFC-11, CFC-12 and CFC-113 in seawater samples using a purge and trap gas-chromatographic system.

We have optimized the analytical parameters of a homemade instrument for the simultaneous measurement of the chlorofluorocarbons CCl(2)F(2) (CFC-12), CCl(3)F (CFC-11) and C(2)Cl(3)F(3) (CFC-113) in seawater. Seawater samples are flame sealed into 60 ml glass ampoules avoiding any contact with the atmosphere and stored in cold, dark condition until analysis. In the laboratory, after cracking the ampoule in an enclosed chamber filled with ultra-pure nitrogen, the seawater sample is transferred to a stripping chamber, where ultra-pure nitrogen is used to purge the dissolved CFCs from the seawater. The extracted gases are then cryogenically trapped, subsequently the trap is isolated and heated and the CFCs are transferred by a carrier gas stream into a precolumn and then are separated on a gaschromatographic packed column. To separate adequately CFC-12 from N(2)O, during the early part of the chromatographic run, the gas stream passes through a molecular sieve, which is then isolated and backflushed. The CFCs are detected on an electron capture detector ((63)Ni ECD). After a careful choice of the experimental conditions, the performances of the system were evaluated. The detection limits for seawater samples are: 0.0081 pmol kg(-1) for CFC-12, 0.0073 pmol kg(-1) for CFC-11 and 0.0043 pmol kg(-1) for CFC-113. The reproducibility of replicate samples lies within 5% for the three CFCs. The system has been successfully employed for CFC measurements in seawater samples collected in the Ross Sea (Antarctica) in the framework of the Italian Antarctic research project.

Cardiotoxicity of Freon among refrigeration services workers: comparative cross-sectional study.

BACKGROUND: Freon includes a number of gaseous, colorless chlorofluorocarbons. Although freon is generally considered to be a fluorocarbon of relatively low toxicity; significantly detrimental effects may occur upon over exposure. The purpose of the present study is to investigate whether occupational exposure to fluorocarbons can induce arterial hypertension, myocardial ischemia, cardiac arrhythmias, elevated levels of plasma lipids and renal dysfunction. METHODS: This comparative cross-sectional study was conducted at the cardiology clinic of the Suez Canal Authority Hospital (Egypt). The study included 23 apparently healthy male workers at the refrigeration services workshop who were exposed to fluorocarbons (FC 12 and FC 22) and 23 likewise apparently healthy male workers (unexposed), the control group. All the participants were interviewed using a pre-composed questionnaire and were subjected to a clinical examination and relevant laboratory investigations. RESULTS: There were no significant statistical differences between the groups studied regarding symptoms suggesting arterial hypertension and renal affection, although a significantly higher percentage of the studied refrigeration services workers had symptoms of arrhythmias. None of the workers had symptoms suggesting coronary artery disease. Clinical examination revealed that the refrigeration services workers had a significantly higher mean pulse rate compared to the controls, though no significant statistical differences were found in arterial blood pressure measurements between the two study groups. Exercise stress testing of the workers studied revealed normal heart reaction to the increased need for oxygen, while sinus tachycardia was detected in all the participants. The results of Holter monitoring revealed significant differences within subject and group regarding the number of abnormal beats detected throughout the day of monitoring (p < 0.001). There were no significant differences detected in the average heart rate during the monitoring period within subject or group. Most laboratory investigations revealed absence of significant statistical differences for lipid profile markers, serum electrolyte levels and glomerular lesion markers between the groups except for cholesterol and urinary beta2-microglobulin (tubular lesion markers) levels which were significantly elevated in freon exposed workers. CONCLUSIONS: Unprotected occupational exposure to chlorofluorocarbons can induce cardiotoxicity in the form of cardiac arrhythmias. The role of chlorofluorocarbons in inducing arterial hypertension and coronary artery diseases is unclear, although significantly elevated serum cholesterol and urinary beta2-microglobulin levels raise a concern.

European emissions of HFC-365mfc, a chlorine-free substitute for the foam blowing agents HCFC-141b and CFC-11.

HFC-365mfc (1,1,1,3,3-pentafluorobutane) is an industrial chemical used for polyurethane foam blowing. From early 2003, HFC-365mfc has been commercially produced as a substitute for HCFC-141b, whose use in Europe has been banned since January 2004. We describe the first detection of HFC-365mfc in the atmosphere and report on a 2 year long record at the high Alpine station of Jungfraujoch (Switzerland) and the Atlantic coast station of Mace Head (Ireland). The measurements at Jungfraujoch are used to estimate the central European emissions of HFC-365mfc, HCFC-141b, and CFC-11. For HFC-365mfc, we estimate the central European emissions (Germany, France, Italy, Switzerland, The Netherlands, Belgium, and Luxembourg) in 2003 and 2004 as 400-500 tonnes year(-1). These emissions are about one-third lower on a per capita basis than what we estimate from the Mace Head measurements for the total of Europe. The estimated emissions of HCFC-141b for central Europe are higher (i.e., 7.2-3.5 ktonnes year(-1)) with a decreasing trend in the period from 2000 to 2004. Residual emissions of CFC-11 are estimated at 2.4-4.7 ktonnes year(-1) in the same time period. The Po Valley (northern Italy) appears to be a main source region for HFC-365mfc and for the former blowing agents HCFC-141b and CFC-11. In 2004, the emissions of HFC-365mfc arose from a wider region of Europe, which we attribute to an increased penetration of HFC-365mfc into the European market.

Total toxicity equivalents emissions of SF6, CHF3, and CCl2F2 decomposed in a RF plasma environment.

Sulfur hexafluorine compound (SF6), trifluoromethane (CHF3) and diclorodifluoromethane (CCl2F2) are extensively used in the semiconductor industry. They are global warming gases. Most studies have addressed the effective decomposition of fluorine compounds, rather than the toxicity of decomposed by-products. Hence, the concepts of toxicity equivalents (TEQs) were applied in this work. The results indicated that HF and SiF4 were the two greatest contributors of TEQ to the SF6/H2/Ar plasma system, while F2 and SiF4 were the two greatest contributors to the SF6/O2/Ar system. Additionally, SiF4 and HF were the two greatest contributors of TEQ to both the CHF3/H2/Ar and CHF3/O2/Ar plasma systems. HF and HCl were the two greatest contributors of TEQ to the CCl2F2/H2/Ar plasma system, and Cl2 and COCl2 were the two greatest contributors to the CCl2F2/O2/Ar system. HCl and HF can be recovered using wet scrubbing, which reduces the toxicity of these emission gases. Consequently, the hydrogen-based plasma system was a better alternative for treating gases that contained SF6, CHF3 and CCl2F2 from the TEQs point of view.

A new design of groundwater sampling device and its application.

Compounds in the atmosphere contaminate samples of groundwater. An inexpensive and simple method for collecting groundwater samples is developed to prevent contamination when the background concentration of contaminants is high. This new design of groundwater sampling device involves a glass sampling bottle with a Teflon-lined valve at each end. A cleaned and dried sampling bottle was connected to a low flow-rate peristaltic pump with Teflon tubing and was filled with water. No headspace volume was remained in the sampling bottle. The sample bottle was then packed in a PVC bag to prevent the target component from infiltrating into the water sample through the valves. In this study, groundwater was sampled at six wells using both the conventional method and the improved method. The analysis of trichlorofluoromethane (CFC-11) concentrations at these six wells indicates that all the groundwater samples obtained by the conventional sampling method were contaminated by CFC-11 from the atmosphere. The improved sampling method greatly eliminated the problems of contamination, preservation and quantitative analysis of natural water.

Transport of hydrocarbons from an emplaced fuel source experiment in the vadose zone at Airbase Vaerløse, Denmark.

An emplaced hydrocarbon source field experiment was conducted in the relatively homogeneous sandy geology of the vadose zone at Airbase Vaerløse, Denmark. The source (10.2 l of NAPL) consisted of 13 hydrocarbons (n-, iso- and cyclo-alkanes and aromates) and CFC-113 as a tracer. Monitoring in the 107 soil gas probes placed out to 20 m from the centre of the source showed spreading of all the compounds in the pore air and all compounds were measured in the pore air within a few hours after source emplacement. Seven of the fourteen compounds were depleted from the source within the 1 year of monitoring. The organic vapours in the pore air migrated radially from the source. The CFC-113 concentrations seemed to be higher in the deeper soil gas probes compared with the hydrocarbons, indicating a high loss of CFC-113 to the atmosphere and the lack of degradation of CFC-113. For the first days after source emplacement, the transport of CFC-113, hexane and toluene was successfully simulated using a radial gas-phase diffusion model for the unsaturated zone. Groundwater pollution caused by the vadose zone hydrocarbon vapours was only detected in the upper 30 cm of the underlying groundwater and only during the first 3 months of the experiment. Only the most water-soluble compounds were detected in the groundwater and concentrations decreased sharply with depth (approximately one order of magnitude within 10 cm depth) to non-detect at 30 cm depth. The groundwater table varied more than 1 m within the measurement period. However that did not influence the direction of the groundwater flow. Approximately 7 months after source emplacement the groundwater table rose more than 1 m within 1 month. That did not cause additional pollution of the groundwater.