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EnSolv and the Environment – Update from the Co Chairman of the United Nations Ozone Assessment panel on nPB.
CONTENT ON THIS PAGE IS RETAINED FOR INFORMATION ONLY
DUE TO n-Propyl bromide now being included in Annex 14 of REACH
EnviroTech Europe Ltd (ETE) continue to publish it as historical information and to record changes occurring in legislation which have affected decisions on formulations and equipment used in vapour degreasing - the most effective, quickest, flexible and cheapest cleaning system used in industry.
EnSolv® invented and patented by EnviroTech has been a market leader all over the world for vapour degreasing. It is based on n-bromopropane (nPB) which now cannot be used as a vapour degreaser within the UK or EU without authorisation.
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Analysis of Status on Science of n-PB Effects on Ozone
White Paper By Don Wuebbles (Department of Atmospheric Sciences – University of Illinois).
November 11, 2014
There is disagreement between the use of scientific information by the European Union and the United Nations Environmental Panel / World Health Organisation (UNEP/WHO) the authority for ozone depletion assessment. Dr. Don Weubbles acknowledged as one of the world authorities on ozone depletion and who Co Chaired the UNEP/WHO 2014 ozone assessment panel explains in detail why the official world study disagrees with the European Union Environment Agency 2014 assessment as not being supported by science.
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Analysis of Status on Science of n-PB Effects on Ozone
Don Wuebbles Department of Atmospheric Sciences University of Illinois Urbana, IL Phone (217) 244-1568 Email:Wuebbles@illinois.edu November 11, 2014 I co-led chapter 5 (with Neil Harris of Cambridge University) of the 2014 WMO-UNEP ozone assessment that is currently in press (the summary, Assessment for Decision Makers, was released in September 2014 (WMO-UNEP, 2014)). Chapter 5, titled Scenarios and Information for Policymakers, of the full assessment, examines the latest understanding of a number of Ozone Depleting Substances (ODSs) including the available analyses of Very Short Lived Substances (VSLS) like n-propyl bromide (n-PB; C3H7Br). The full assessment will be released in early 2015 as a web-based report. In Chapter 5 of the full assessment, we include the following text related to the evaluation of VSLS like n-PB: Table 5-3 shows analyses of the spatial dependence in ODPs for VSLS primarily based on results using different versions of the NCAR global 3-D model (Wuebbles et al., 2009, 2011; Patten and Wuebbles, 2010; Youn et al., 2010; Patten et al., 2011). Note that this model calculates an atmospheric lifetime of 53.7 years for CFC-11, so the published ODPs would not be significantly affected by the revised SPARC (2013) lifetime for CFC-11. In these studies, the VSLS examined all have quite small ODPs based on emissions occurring primarily at midlatitudes. New approaches for estimating VSLS ODPs have been developed since WMO (2011) based on Lagrangian models (Tegtmeier et al., 2012; Pisso et al., 2010; Brioude et al., 2010), with similar findings to previous studies, except for emissions in the tropics where a different treatment of convection may allow for more VSLS (and their products) to reach the stratosphere. The reported atmospheric lifetime and Ozone Depletion Potential (ODP) for n-PB in Table 5-3 for midlatitude emissions (30-60N), based on the 3-D chemistry-climate modeling studies of Wuebbles et al. (2011), are 24.7 days and 0.0049, respectively. At the same time, we noted: Earlier studies (Wuebbles et al., 1999, 2001; Olsen et al., 2000; Bridgeman et al., 2000) have shown that the ODPs for short-lived compounds depend greatly on when or where the emissions occur, with the largest ODPs being found for emissions in the tropics. Although it is generally expected that most emissions from anthropogenic emissions of VSLS will occur at Northern midlatitudes, there is no guarantee of this and the locations of future emissions could change. In addition, we also reported upon an indirect study of the ODP using a semi-empirical approach based on the Lagrangian model analysis of Brioude et al. (2010). The results in Table 5-4 of WMO-UNEP Chapter 5 are taken from the Supplementary materials for that published paper. The results in Table 5-4 are quite a bit higher than Wuebbles et al. (2011) and show an ODP for n-PB of 0.0235 (0.0150-0.032) for North America emissions and 0.0150 (0.0070-0.0260) for European emissions. However, as noted in the chapter, the Brioude et al. results may be an overestimate because they do not properly account for reaction loss in the troposphere and therefore may have overestimated the amount of n-PB reaching the stratosphere. As stated in the Chapter: The recent modeling studies also re-emphasize the point that VSLS ODPs are very dependent on the location of emissions, and not just the latitude; for example, by co-location with efficient vertical transport by deep convection into the stratosphere (semi-empirical ODPs as a function of specific locations of emissions based on Brioude et al. (2010) are shown in Table 5-4). Brioude et al. (2010) showed that these factors are more important than regional variations in VSLS losses by OH or photolysis. Using CO-like emissions to represent anthropogenic VSLS, they estimated ODPs for various compounds and found maximum ODPs over the Indian sub-continent varying from 0.079 in winter to 0.29 in summer for n-propyl bromide (C3H7Br or nPB) and from 0.13 in winter to 0.83 in summer for CH3I. Pisso et al. (2010) applied their new methodology to an nPB-like tracer with a lifetime of 20 days. They also found higher ODPs over southeast Asia in the summer (and over western Pacific in winter). In July in the tropics (30°N-30°S), ODPs varied from 0.33 in runs with convection to 0.17 in runs with no convection. Locally, values over southeast Asia are as high as 1.00. In general the results from these Lagrangian studies predict higher ODPs regionally compared to the global model results. These differences highlight uncertainties in simulating the transport of VSLS, with boundary layer mixing, convection depth and advection strength all possibly leading to local differences in VSLS delivery to the stratosphere (e.g., see Hossaini et al., 2012b; Feng et al., 2011; Hoyle et al. 2011). The global model studies (e.g., Wuebbles et al., 2011) used a full chemical treatment for VSLS and CFC-11 degradation in the stratosphere and more realistic degradation and wet deposition schemes for VSLS in the troposphere than the Lagrangian based studies (e.g., Tegtmeier et al., 2012; Pisso et al., 2010), leading to less VSLS reaching the stratosphere. Overall, these results point to potentially more important impacts from VSLS if emissions occur in regions close to convective regions in the tropics. The 2014 report from the European Environment Agency, Ozone-Depleting Substances 2013, examines the European reporting requirement for n-PB and determines a total import of nPB to Europe of 1014.3 metric tonnes and a weighted ODP-tonnes for imported nPB of 101.4. This suggests they used an ODP of 0.1 for n-PB. This is far too large by either the Wuebbles et al. (2011) or the Brioude et al. (2010) analyses by roughly a factor of 6.7 for Europe emissions using the Brioude et al approach and a factor of 20.4 using the Wuebbles et al. 3-D model results. Because Wuebbles et al. may have underestimated the convection based on the observations used in the Brioude et al. study, the reality is likely somewhere between the two results, but this still suggests that the European Environment agency still used an ODP a factor of 10 or more too large. The science does not support the ODP used by the European Environment Agency. References Bridgeman, C.H., J.A. Pyle, and D E. Shallcross, A three-dimensional model calculation of the ozone depletion potential of 1-bromopropane (1-C3H7Br), J. Geophys. Res., 105, 26,493-26,502, 2000. Brioude, J., R.W. Portmann, J.S. Daniel, O.R. Cooper, G.J. Frost, K.H. Rosenlof, C. Granier, A.R. Ravishankara, S.A. Montzka, and A. Stohl, Variations in ozone depletion potentials of very short-lived substances with season and emission region, Geophys. Res. Lett., 37, L19804, doi: 10.1029/2010GL044856, 2010. European Environment Agency, 2014: Ozone-Depleting Substances 2013. EEA Technical Report No. 14/2014, Copenhagen. Olsen, S.C., B.J. Hannegan, X. Zhu, and M.J. Prather, Evaluating ozone depletion from very short-lived halocarbons, Geophys. Res. Lett., 27, 1475-1478, 2000. Patten, K.O., and D.J. Wuebbles, Atmospheric lifetimes and Ozone Depletion Potentials of trans-1-chloro-3,3,3-trifluoropropylene and trans-1,2-dichloroethylene in a three-dimensional model, Atmos. Chem. Phys., 10, 10867-10874, 2010. Patten, K.O., V.G. Khamaganov, V.L. Orkin, S.L. Baughcum, and D.J. Wuebbles, OH reaction rate constant, IR absorption spectrum, ozone depletion potentials and global warming potentials of 2-bromo-3,3,3-trifluoropropene, J. Geophys. Res., 116, D24307, doi:10.1029/2011JD016518, 2011. Pisso, I., P.H. Haynes, and K.S. Law, Emission location dependent ozone depletion potentials for very short-lived halogenated species, Atmos. Chem. Phys., 10, 12025-12036, 2010. SPARC (Stratospheric Processes And their Role in Climate), Report on the lifetimes of stratospheric ozone-depleting substances, their replacements, and related species, M. Ko, P. Newman, S. Reimann, S. Strahan (Eds.), SPARC Report No. 6, WCRP-15, Zurich, Switzerland, 2013 Tegtmeier, S., K. Krüger, B. Quack, E.L. Atlas, I. Pisso, A. Stohl, and X. Yang, Emission and transport of bromocarbons: from the West Pacific ocean into the stratosphere, Atmos. Chem. Phys., 12, 10633-10648, doi:10.5194/acp-12-10633-2012, 2012. WMO-UNEP (coauthor), 2014: Assessment for Decision-Makers: Scientific Assessment of Ozone Depletion 2014. WMO Global Ozone Research and Monitoring Project – Report No. 56, Geneva, Switzerland; also available on WMO website. Wuebbles, D.J., K.O. Patten, M.T. Johnson, and R. Kotamarthi, New methodology for Ozone Depletion Potentials of short-lived compounds: n-Propyl bromide as an example, J. Geophys. Res., 106, 14551-14771, 2001. Wuebbles, D.J., D. Youn, K. Patten, D. Wang, and M. Martinez-Aviles, Metrics for ozone and climate: Three-dimensional modeling studies of Ozone Depletion Potentials and Indirect Global Warming Potentials, in Twenty Years of Ozone Depletion, C. Zerefos, G. Contopoulos, and G. Skalkeas, editors, Springer Publishing, Dordrecht, The Netherlands, doi: 10.1007/978-90-481-2469-5, p. 297-326, 2009. Wuebbles, D.J., K. Patten, D. Wang, D. Youn, M. Martínez-Avilés, and J. Francisco, Three-dimensional model evaluation of the Ozone Depletion Potentials for n-propyl bromide, trichloroethylene and perchloroethylene, Atmos. Chem. Phys., 2011, 11, 2371-2380, 2011. Youn, D., K.O. Patten, D.J. Wuebbles, H. Lee, and C.-W. So, Potential impacts of iodinated replacement compounds CF3I and CH3I on atmospheric ozone: a three-dimensional modeling study, Atmos. Chem. Phys., 10, 10129-10144, 2010.We can provide you with a Material Safety Data Sheets, independent laboratory reports, product samples and technical assistance.
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Oxygen Cleaning
Cleaning For Oxygen Service Whitepaper
White Paper By Phil Dale (Co-contributor Handbook for Critical Cleaning – Liquid Displacement Drying Techniques).
Cleaning for oxygen service is best defined as the removal of combustible contaminants from the surface of any equipment or system in oxygen service, including all parts thereof. Essentially, any component that may come into contact with an oxygen rich environment.
The combustible contaminants include organic and inorganic substances such as hydrocarbon material for example oils and greases, paper, fibre, coal dust, solvents, weld slag, rust, sand and dirt. If these contaminants are not removed properly, in a worst case scenario, this can cause combustion in an oxygen atmosphere or at the least rejection of the product due to unacceptable product purity.
Oxygen in its own right is not flammable but it supports combustion. Oxygen can react with most materials. The higher the oxygen content and/or pressure in a system the more vigorous the combustion and the lower the ignition temperature required. Materials that do not normally ignite in atmospheric air will burn and may explode in an oxygen rich environment. In addition the oxygen rich environment will give rise to a higher flame temperature and combustion velocity and the devastating consequences thereof.
The recognition of oxygen’s reactivity has led to stringent requirements regarding the cleanliness of equipment in oxygen service. Strict guidelines exist to ensure that care must be taken in the selection of equipment including all materials and components, all of which need to be oxygen compatible. They must also be free from combustible contaminants as described above.
With this in mind special consideration must be given to any cleaning processes employed in the manufacture and maintenance of all oxygen service systems.
Specific consideration must be given to the following:
- cleaning standard to be achieved (how clean is clean?)
- cleaning procedure specified (or not)
- cleaning agent to be used
- surface properties of the parts to be cleaned
- shape and geometry of the material
- types and amounts of contaminants
- the degree of automation required
The size and capacity of the equipment is determined from:
- the size of the material or components to be cleaned
- the required throughput
Your starting point should be the cleaning standard and procedure. For example *G93 indicates that solvent cleaning is preferable. Solvent cleaning and solvent vapour phase cleaning of components consists of the removal of contaminants by immersion in the solvent, possibly with the addition of ultrasonic agitation and the action of continued condensation of solvent vapour on the component surfaces. The procedure requires that the oxygen equipment, system or component is colder than the solvent boiling point. This allows the vapour to condense on the components and perform a final rinse.
The major significant advantage of solvent cleaning is that re-vaporised solvent is always clean and the contaminants remain in the evaporator liquid section which requires only periodic cleaning out, thus causing a reduction in the frequency of system downtime.
It is also important to note **G127–95 (Reapproved 2000). The effectiveness of a particular cleaning agent depends upon the method by which it is used, the nature and type of the contaminants and the characteristics of the article being cleaned, such as size, shape, and material. Final evaluation of the cleaning agent should include testing of actual products and production processes.
All equipment must, together with the cleaning chemistry, fulfil as a minimum the legislation for health, safety and environment.
The choice of equipment has to be based on the efficiency of cleaning versus cost bearing in mind what is the cost of the problem? If there is no cost there is no problem.
The efficiency is controlled by utilising typical samples, written procedures and requested criteria for cleanliness.
If you need to clean to ASTM G93 – 03(2011) Standard Practice for Cleaning Methods and Cleanliness Levels for Material and Equipment Used in Oxygen-Enriched Environments then all of the above needs to be given due consideration.
*G93 – Standard Practice for Cleaning Methods and Cleanliness Levels for Material and Equipment Used in Oxygen-Enriched Environments
**Designation: G127 –95(Reapproved 2000) Standard Guide for the Selection of Cleaning Agents for Oxygen Systems.
Handbook for Critical Cleaning, Second Edition – 2 Volume Set Hardcover – April 4, 2011by Barbara Kanegsberg (Editor), Edward Kanegsberg (Editor)
We can provide you with a Material Safety Data Sheets, independent laboratory reports, product samples and technical assistance.
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New study disputes TLV for nPB
A detailed comprehensive review of 1-bromopropane studies confirm current recommendations by EnviroTech for occupational exposure levels for safe usage of EnSolv® as a vapour degreasing solvent.
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Update on a safe occupational exposure level for 1-Bromopropane
Prepared for EnviroTech Europe, Ltd.
Prepared by Dr. Mark Stelljes
SLR International Corporation
September 2014
Executive Summary
This paper re-evaluates EnviroTech Europe’s (ETE’s) current occupational exposure level recommendation of 100 ppm for 1-bromopropane (1-BP) [106-94-5] in the vapor degreasing industry in light of the recent lowering of the ACGIH Toxicity Threshold Value (TLV) from 10 ppm to 0.1 ppm. The 0.1 ppm value is based on a study of 86 workers exposed to 1-BP during its manufacturing in China in four different facilities. The authors reported significant effects at all 1-BP exposure levels down to 1.28 ppm. The 1-BP in these facilities had concentrations of the isomer 2-bromopropane [75-26-3] (2-BP) present as a contaminant at about 10-20 times the level sold for vapor degreasing.
There are several factors that undermine the conclusions reached in the paper that a concentration of 1.28 ppm resulted in toxicity in exposed workers. These factors were related to:
(1) Exposure measurements – passive rather than active samplers were used, and concentrations varied by more than tenfold for the same activity.
(2) Exposure via other routes in addition to inhalation – described worker activities indicate substantial dermal exposure, which increases the overall dose of the chemical relative to just inhalation exposure.
(3) Exposure to other chemicals – at least 20% of the workers were previously exposed to 2-bromopropane
(2-BP), and no testing was done for other chemical exposure.
(4) Statistical methods and interpretations – instead of using paired patient-exposure data, authors categorized exposure into groups (e.g., high, low); this resulted in apparent statistical relationships that may not be biologically relevant.
(5) Lack of robust dose-response relationships – when evaluating typical doseresponse relationships, only a single parameter (vibration sense in the toes, a subjective parameter) was shown to be significantly different across all dose levels.
(6) The outcome of the subjective vibration sense test was in part dependent on the testing doctor – this dependency should remove the test and its results from consideration in the paper as a scientifically defensible endpoint.
When all of this information is considered as a whole, it is unlikely that the 1.28 ppm lowest effect concentration reported in the paper is accurate. The interpretations in the Li et al. study are inconsistent with expectations based on the ways in which 1-BP acts in rodents relative to humans. Studies on how 1-BP acts in the body of rats and mice and studies on metabolism of the chemical in humans indicate that humans should be no
more sensitive to 1-BP than either of these rodents.
Based on the weight of evidence available for the toxicity of 1-BP in humans and rodents, there is no credible scientific reason to target an occupational concentration as low as 10 ppm or 0.1 ppm. ETE’s current recommendation of 100 ppm should be maintained, and employers together with vapor degreasing personnel should not be concerned about the much lower levels recommended by the ACGIH.
We can provide you with a Material Safety Data Sheets, independent laboratory reports, product samples and technical assistance.
For more information or advice please telephone us on +44 (0) 20 8281 6370 or use our contact form.
All products are supplied and supported by EnviroTech Europe Ltd. Manufactured in the United Kingdom and available on short delivery times through our dedicated team of distributors worldwide.
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