TESTING ACETATE-BASED DE-ICING CHEMICALS IN FINLAND …

TESTING ACETATE-BASED DE-ICING CHEMICALS IN FINLAND FOR RAILWAY SURROUNDINGS IN

2012

Site: VR Track Oy, Ilmala Railway Yard and Tampere Railway Station

Tapio Raukola

17th of September, 2012

TABLE OF CONTENTS Page 1 BACKGROUND AND INTRODUCTION 1 2 STORMWATER SAMPLING FROM HOLE K201 2 3 GROUNDWATER SAMPLING TUBE PVP1 5 4 RESULTS 7 5 PERFORMANCE OF TESTED CHEMICALS 8

Ilmala Railway Yard 8

Tampere Railway Station 11 6 FUTURE PROSPECTS FOR RAILWAYS WINTER MAINTENANCE 13 ANNEXES

1 RESULTS 14

2 MODEL SHEET OF FOLLOW-UP TABLE 24

1 Testing acetate-based de-icing chemicals in 2012 for railway surroundings at Ilmala Railway Yard, Helsinki and Tampere Railway

Station, Finland, 17th

of September, 2012.

TESTING ACETATE-BASED DE-ICING CHEMICALS FOR RAILWAY SURROUNDINGS IN 2012 AT ILMALA RAILWAY YARD

1 BACKGROUND AND INTRODUCTION VR TRack Oy and MK Trading A.S agreed to carry out tests with acetate-based de-icing chemicals in the Ilmala railway yard, which belongs to the Finnish Transport Agency Maintenance Area 1 in Helsinki. The objective of the testing was to find proper, safe and effective chemicals for ice control activities in railway surroundings: switches, platforms and level crossings for roads. The Finnish Transport Agency authorized in December 2011 MK Trading test the chemicals defined in the MK Trading application. According to the terms the applicant had to organize a follow-up in the area to find out possible impacts of the tested chemicals on storm water. A small-scale testing was also included in the permit in the Tampere Railway Station, but no environmental follow-up was required there. The Ilmala railway yard exists on an old refuse area filled with gravelly materials. Due to the history its storm-water quality has been critical and a regular water sampling is being carried out using permanent observation facilities. If the storm water quality is not good enough to be let to the drainage system, it must be treated. The permit for testing was given for three chemicals, granular calcium-magnesium-acetate (CMA), granular sodium-acetate (NaAc) and liquid potassium-acetate CF7. The tested chemicals were manufactured by Cryotech Ltd. U.S. and they are described in detail on www.mktrading.no. The testing plan was prepared, the samplings taken and the results reported by Golder Associates Oy. The same company also carries out the long-term follow-up of Ilmala railway yard as mentioned above. The water samples for the MK Trading tests were taken from two permanent water collection facilities, K201 and PVP1, which are illustrated below. This report briefly describes the testing procedures and test results, usage of the chemicals and gained experiences from them, evaluates how effective they were in use and envisions future prospects, if a permanent permit that facilitates.

http://www.mktrading.no/



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2 STORMWATER SAMPLING FROM HOLE K201

Location and collection of sample

The sampling hole K201 is located aside the Ilmala railway yard near the Shell petrol station. It is about 5.5 m deep. All storm waters of Ilmala yard run through it and further via Kumpulanpuro stream to the sea. In addition to the routine water control analyses included in the long term follow-up, possible acetates and oxygen depletion were considered essential to be determined from the samples. However, oxygen depletion was often determined from routine samples. The samples from K201 were collected with a pump during 24 hours. The pump took a little water at every 15 minutes. Samples for de-icing chemicals and other purposes were taken from the same main sample. Samples taken The background sample from K201 was taken before the use of the chemicals on the 28th of December 2011, the second one on the 25th of January 2012 and the third one on the 19th of April 2012. The last, fifth, sample was taken on the 4th of September 2012.

Photo 1: The storm water sampling hole, K201. The collector pump is seen on the left of the sample taker.



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Photo 2: The sample after collection. On 25th of January 2012 the colour was brown as rust.

Photo 3: K201 is about 5.5 m deep. All storm waters from Ilmala railway yard run through it.



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. Photo 4: The samples are ready for a delivery to the laboratory. Major part of these samples is for routine purposes.



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3 GROUNDWATER SAMPLING TUBE PVP1 The PVP1 sampling tube locates near a level crossing that belonged to the testing programme. Also PVP1 was used for both routine sampling and acetate impact testing. PVP1 is 6.3 m deep and the water surface in it was 2.4 m from the top of the tube on the 22nd of February 2012. Soil around the tube is silt on the bottom part. On top of the silt there are gravelly construction layers. There is also a clayey bottom-soil area in the railway yard. When the water sample was taken, water was first pumped away from the tube three times the volume of the tube water-volume. After that the sample was taken from the replacement water.

Photo 5: Groundwater sampling tube PVP1 in Ilmala Railway Yard. The pump is emptying water from the tube before sampling.



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Photo 6: Samples on the 22nd of February have been taken. Colour of the water was grey.



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4 RESULTS The results from analyses of the samples are in Annex 1. The only finding has been from the groundwater sample taken from PVP1 on the 22nd of February 2012. It included acetates 12 mg/l. Quality of the storm water was of primary importance in this study (K201 samples), but no impacts of the used chemicals were found.



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5 PERFORMANCE OF TESTED CHEMICALS Ilmala railway yard The Finnish Transport Agency authorized MK Trading to carry out testing with VR Track Oy at the Ilmala Railway Yard for a service platform, a couple of road level crossings and a few switches. At the switches chemicals were especially tested for cross pieces. At the beginning only granular materials CMA and NaAc were used. After experiencing them, CF7 (potassium liquid) tests were started on the second half of February. Chemicals were used for events such as freezing rain, snowfall and ice >1mm thick. The weather phenomena occurred during 11.-12.01.12, 13.-14.02.12 and 25.-28.02.12. In addition chemicals were spread onto switches for fallen snow clumps, for preventative actions for snowfall and ice forming, for level crossing flange-ways and for removing snow from a level crossing and its approach roads. Before the tests MK Trading gave a follow-up form to be filled in for evaluations (an empty model is in Annex 2). In that success was to be rated between 1 and 5, 1 indicating a very poor performance and 5 excellent. General characteristics of the tested chemicals CMA and NaAc pellets start penetrating through snow and ice as soon as they are spread. After penetrating to the bottom snow and ice layers are full of holes and the pellets then start loosening bonded snow and ice. This phenomenon is different from many other common de-icing chemicals (salt, urea, for instance). If CMA and NaAc are spread preventatively, pellets get sticky from moisture of the ambient air and ground, and do not easily fly away from the place of spreading. If necessary, pellets can be wetted with water or CF7 to increase their sticky properties. Electric conductivity of these chemicals is about half or less from that of the common road salt (NaCl). Corrosion they cause is about the same as that of tap water, so they are safe to use on concrete. Special observations during the tests Some observations below, done by the responsible supervisor in Ilmala, describe effectiveness of the tested chemicals. They confirm the functioning pattern mentioned in the paragraph above. On the service platform trains were tanked with water, which splashed onto the platform forming thick ice. NaAc was able to penetrate through it, break the ice and then friable ice could be removed.



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Photo 7: The service platform. Ice has not yet been melted with NaAc. After melting operation the platform became bare of snow and ice.

On flange-ways of the level crossings pellets penetrated through hard layers of snow/ice, and then the first passing train smashed them into grains or like hailstones. Thus the broken snow/ice was easy to swipe away even by finger.

Photo 8: Level crossing made of wood. Flange-ways are free of snow and ice.



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Photo 9: Level crossing covered with rubber. Flange-ways are clean.

Once hundreds of cubic metres of snow was removed from a road level crossing and its approaches with a help of CMA and NaAc pellets. Again pellets penetrated through snow, and the chemicals made the snow soft and easy to remove. On the switch cross pieces pellets penetrated through snow clumps, and sometime after spreading the switches were clean and remaining pellets were lying on the bottom influencing in a preventative manner for the next falling snow and ice. The same way pellets remained active on the bottom if they were spread preventatively. The liquid de-icer CF7 also had a long-lasting and sticky effect after spreading onto switches.



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Photo 10: Pellets have been effective in a cross-piece of a switch. Snow and ice clumps have melted. Partly melted pellets can be seen on the bottom where they are ready for the next possible event.

It was also observed that places where the test chemicals were used soon became dry and dust problems were less. According to the responsible supervisor of VR Track Oy in Ilmala, performance of all three chemicals was rated excellent (5) in all tested circumstances. Thus, no manual cleaning was needed where the chemicals were used. It can be concluded that the staff earlier used for manual snow and ice removal can be used for more productive maintenance work, if CMA, NAAC and CF7 are used as in the tests. The consequence is that trains can better travel according to the time table in wintry conditions. The materials were used the following amounts:

CMA 1700 kg

NaAc 1000 kg

CF7 50 litres. Tampere railway station Included in the authorization of the Finnish Transport Agency, but excluded from the environmental testing described above, was the use of CMA and NaAc at the Tampere railway station. The chemicals were used for the cold tunnel stone-slab floor (CMA) under the person traffic rails, and on the stone-made stairs (mainly NaAc) between the tunnel and the platforms. To a limited amount they were also used on the platforms for easing ice removal from surface drains. The results were excellent in all tested circumstances. The tunnel floor, for instance, gets easily slippery of concentrated moisture. This problem was taken away with the chemicals.



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The total use of CMA in Tampere was 375 kg and that of NaAc 1000 kg.

Photo 11: There was no slipperiness on the floor of the cold tunnel during the winter after starting using de-icing chemicals (CMA).

Photo 12: The chemicals were effective also on the stairs. Here a good grip and just a moist surface can be seen. Mainly NaAc was spread for the stairs.



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6 FUTURE PROSPECTS FOR RAILWAYS WINTER MAINTENANCE If the Finnish Transport Agency allows a permanent use of CMA, NaAc and CF7 all over Finland for railway surroundings, it offers the railway maintenance contractors an excellent tool for combatting snow and ice on platforms, stairs, cold tunnels, switches and level crossings. The chemicals seem to be of great help in assuring safe and timely winter traffic on rails. Expenses can be reduced, too. There are tens of busy enough railway yards in Finland where the tested chemicals could be utilised. If one man can be freed for only one month period to do more productive maintenance work, roughly two tons of these chemicals can be procured with the employer salary savings. It would mean that during four months period about 8 tons could be procured. If one man could be saved in say 50 railway yards, about 400 tons would be procured without extra costs. Excess chemicals can be easily stored to the next winter when kept in dry conditions. In Ilmala the total use of chemicals was about 2.7 tons during less than 3 months when spreading was allowed only for pre-named, limited objects. It can be assumed that the need for a railway yard such as Ilmala would be around 10 tons per winter, if the permanent permit allowed an unlimited use of them. Conditions of different winters have their varying influence, of course. According to the information from VR Track Ltd, no manpower was needed in Ilmala for cleaning snow and ice where chemicals were spread. It meant savings, and a good service level fast.



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ANNEX 1 RESULTS OF LABORATORY ANALYSES



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Ensimmäinen näyte, taustanäyte K201, 28.12.2011 First, background sample before testing, on 28th of Dec. 2011, Report



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Report

Page 2 (2) K1100905

PSHFHRFQ3L __________________________________________________________________

ALS Finland Oy Ruosilankuja 3 E 00390 Helsinki

Finland www.alsglobal.fi

[email protected] Tel: + 358 10 470 1200 Fax: + 358 10 470 1201

Raportti on hyväksytty ja digitaalisesti allekirjoitettu

* =näyte tutkittu ei-akkreditoidulla menetelmällä.

Menetelmäkuvaus Method description 1 Asetaatin määritys. Acetate. Tulosten raportointi etikkahappona. Derivatisoinnin jälkeen etikkahapon määritys

headspace GCMS- menetelmää käyttäen. Menetelmä on akreditoittu.

2 pH:n määritys vedestä ja liuoksista CSN ISO 10523 mukaan. pH of water.

Hyväksyjä SUAB Suzana Abenet

Analysoija1 1 Analysoinnista vastaa GBA, Flensburger Strasse 15, 25421 Pinneberg, Saksa, joka on akkreditoitu saksalaisen

akkreditointielimen DAR toimesta (numero DAC-P-0040-97-10). 2 Analysoinnista vastaa ALS Czech Republic, s.r.o., Na Harfê 336/9, 190 00, Praha 9, Tšekki, joka on akkreditoitu

tšekkiläisen akkreditointielimen CAI toimesta (numero L 1163). Laboratoriot sijaitsevat Prahassa (Na Harfê 336/9, 190 00, Praha 9), Ceska Lipassa (Bendlova 1687/7, 470 03 Ceska Lipa) ja Pardubicessa (V Raji 906, 530 02

Pardubice). Mittausepävarmuus on ilmoitettu laajennettuna mittausepävarmuutena, jossa on käytetty kattavuuskerrointa 2,

jolloin luotettavuustaso on noin 95%. Level of confidence.

Alihankkijoiden mittausepävarmuus on yleensä annettu laajennettuna mittausepävarmuutena, jossa on käytetty kattavuuskerrointa 2. Laboratoriolta saa lisätietoja pyydettäessä.

Analyysitulokset pätevät ainoastaan analysoiduille näytteille. Lausunto ei kuulu akkreditoinnin piiriin. Tutkimusraportin saa kopioida vain kokonaan. Muussa tapauksessa kopioinnista on saatava lupa laboratoriolta.

Koskien laboratorion vastuita ks. voimassa oleva tuoteluettelo tai www.alsglobal.fi Kopio lähetetty tiedoksi:

, Golder Associates Oy, 00390 HELSINKI, Finland. Vain digitaalisesti alekirjoitettu PDF- raportti on alkuperäinen. Kaikki muut printatut versiot ovat kopioita.

1 Analyysin suorittava yksikkö (ALS Finland Oy:ssä) tai laboratorio (alihankkija).



of September, 2012.

Toinen näyte K201, 25.1.2012 Second sample K201 on 25th of Jan. 2012, Report



of September, 2012.

Report

Page 2 (2) K1200037

S380EKG29T __________________________________________________________________





* =näyte tutkittu ei-akkreditoidulla menetelmällä. Menetelmäkuvaus Method description

1 pH:n määritys vedestä ja liuoksista CSN ISO 10523 mukaan. pH of water. 2 BOD7:n (BOD määritys 7 päivän jälkeen) määritys vesinäytteistä CSN EN 1899-1 mukaan laimentamalla ja

lisäämällä ymppiä + ATU:a (allyylitiourea). BOD7:n määritys vesinäytteistä CSN EN 1899-2 mukaan laimentamattomalle näytteelle.

3 Asetaatin määritys. Acetate. Tulosten raportointi etikkahappona. Derivatisoinnin jälkeen etikkahapon määritys headspace GCMS-

menetelmää käyttäen. Menetelmä on akreditoittu. Hyväksyjä

SUAB Suzana Abenet Analysoija1

1 Analysoinnista vastaa ALS Czech Republic, s.r.o., Na Harfê 336/9, 190 00, Praha 9, Tšekki, joka on akkreditoitu tšekkiläisen akkreditointielimen CAI toimesta (numero L 1163). Laboratoriot sijaitsevat Prahassa (Na Harfê 336/9,

190 00, Praha 9), Ceska Lipassa (Bendlova 1687/7, 470 03 Ceska Lipa) ja Pardubicessa (V Raji 906, 530 02 Pardubice).

2 Analysoinnista vastaa GBA, Flensburger Strasse 15, 25421 Pinneberg, Saksa, joka on akkreditoitu saksalaisen akkreditointielimen DAR toimesta (numero DAC-P-0040-97-10).

Mittausepävarmuus on ilmoitettu laajennettuna mittausepävarmuutena, jossa on käytetty kattavuuskerrointa 2, jolloin

luotettavuustaso on noin 95%. Level of confidence. Alihankkijoiden mittausepävarmuus on yleensä annettu laajennettuna mittausepävarmuutena, jossa on käytetty

kattavuuskerrointa 2. Laboratoriolta saa lisätietoja pyydettäessä. Analyysitulokset pätevät ainoastaan analysoiduille näytteille. Lausunto ei kuulu akkreditoinnin piiriin.

Tutkimusraportin saa kopioida vain kokonaan. Muussa tapauksessa kopioinnista on saatava lupa laboratoriolta. Koskien laboratorion vastuita ks. voimassa oleva tuoteluettelo tai www.alsglobal.fi

Kopio lähetetty tiedoksi: , Golder Associates Oy, 00390 HELSINKI, Finland.

+ [email protected]

Vain digitaalisesti alekirjoitettu PDF- raportti on alkuperäinen. Kaikki muut printatut versiot ovat kopioita. 1 Analyysin suorittava yksikkö (ALS Finland Oy:ssä) tai laboratorio (alihankkija).



of September, 2012.

Kolmas näyte PVP1, 22.2.2012 Third sample PVP1 on 22nd of Feb. 2012

Report Page 1 (2) K1200076

U4JLR3Y1R5 __________________________________________________________________





Golder Associates Oy Projekti 11 502 13 0415 Jari Mattila

Tilausnumero Sisäänkirjattu 2012-02-22 Ruosilankuja 3 E

Raportoitu 2012-03-01 00390 HELSINKI Finland

Veden analysointi Water analysis

Asiakkaan tunnus CMA1, PVP1

22.2.2012 Näytenumero H10005446

Analyysi Tulos Yksikkö Menetelmä Analysoija Allekirjoitus

asetaatti etikkahappona* 12 mg/l 1 1 SUAB acetate as acetic acid 12 mg/l



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1 Asetaatin määritys. Tulosten raportointi etikkahappona. Derivatisoinnin jälkeen etikkahapon määritys headspace GCMS-

menetelmää käyttäen. Menetelmä on akreditoittu. Hyväksyjä

SUAB Suzana Abenet Analysoija1

1 Analysoinnista vastaa GBA, Flensburger Strasse 15, 25421 Pinneberg, Saksa, joka on akkreditoitu saksalaisen

akkreditointielimen DAR toimesta (numero DAC-P-0040-97-10). Analyysitulokset pätevät ainoastaan analysoiduille näytteille. Lausunto ei kuulu akkreditoinnin piiriin.

Tutkimusraportin saa kopioida vain kokonaan. Muussa tapauksessa kopioinnista on saatava lupa laboratoriolta.

Koskien laboratorion vastuita ks. voimassa oleva tuoteluettelo tai www.alsglobal.fi Kopio lähetetty tiedoksi:

, Golder Associates Oy, 00390 HELSINKI, Finland. Vain digitaalisesti alekirjoitettu PDF- raportti on alkuperäinen. Kaikki muut printatut versiot ovat kopioita.



of September, 2012.

Neljäs näyte K201, 19.4.2012

Fourth sample K201, on 19th of Apr. 2012


YYSTDMBI8E __________________________________________________________________





Golder Associates Oy Projekti 11 502 13 0415 Helena Railo


Raportoitu 2012-04-27 00390 HELSINKI

Veden analysointi Water analysis Asiakkaan tunnus CMA-2 K201

18.-19.04.2012 Näytenumero H10006452

Analyysi Tulos Mittausepävarmuus (±) Yksikkö Menetelmä Analysoija Allekirjoitus

pH 7.55 0.08 1 1 SUAB

asetaatti etikkahappona <2,0 mg/l 2 2 SUAB acetate as acetic acid <2.0 mg/l



of September, 2012.


YYSTDMBI8E __________________________________________________________________






1 pH:n määritys vedestä ja liuoksista CSN ISO 10523 mukaan. pH of water. 2 Asetaatin määritys. Acetate. Tulosten raportointi etikkahappona. Derivatisoinnin jälkeen etikkahapon

määritys headspace GCMS- menetelmää käyttäen. Menetelmä on akreditoittu.


Analysoija1 1 Analysoinnista vastaa ALS Czech Republic, s.r.o., Na Harfê 336/9, 190 00, Praha 9, Tšekki, joka on

akkreditoitu tšekkiläisen akkreditointielimen CAI toimesta (numero L 1163). Laboratoriot sijaitsevat Prahassa (Na Harfê

336/9, 190 00, Praha 9), Ceska Lipassa (Bendlova 1687/7, 470 03 Ceska Lipa) ja Pardubicessa (V Raji 906, 530 02

Pardubice). 2 Analysoinnista vastaa GBA, Flensburger Strasse 15, 25421 Pinneberg, Saksa, joka on akkreditoitu

saksalaisen akkreditointielimen DAR toimesta (numero DAC-P-0040-97-10).


luotettavuustaso on noin 95%. Level of confidence. Alihankkijoiden mittausepävarmuus on yleensä annettu laajennettuna mittausepävarmuutena, jossa on

käytetty kattavuuskerrointa 2. Laboratoriolta saa lisätietoja pyydettäessä.

Analyysitulokset pätevät ainoastaan analysoiduille näytteille. Lausunto ei kuulu akkreditoinnin piiriin. Tutkimusraportin saa kopioida vain kokonaan. Muussa tapauksessa kopioinnista on saatava lupa

laboratoriolta. Koskien laboratorion vastuita ks. voimassa oleva tuoteluettelo tai www.alsglobal.fi


+ [email protected]

Vain digitaalisesti alekirjoitettu PDF- raportti on alkuperäinen. Kaikki muut printatut versiot ovat kopioita. 1 Analyysin suorittava yksikkö (ALS Finland Oy:ssä) tai laboratorio (alihankkija).



of September, 2012.

Viides näyte K201, 4.9.2012

Fifth Sample K201, 4th of Sept, 2012


1AW8Q68G0ZZ __________________________________________________________________





Golder Associates Oy Projekti 11 502 13 0415 Helena Railo


Raportoitu 2012-09-14 00390 HELSINKI Veden analysointi Water analysis

Asiakkaan tunnus CMA-3 K201 4.9.2012

Näytenumero H10009208 Analyysi Tulos Mittausepävarmuus (±) Yksikkö Menetelmä Analysoija Allekirjoitus

pH 7.75 0.08 1 1 SUAB asetaatti etikkahappona* <2.0 mg/l 2 2 SUAB

acetate as acetic acid <2.0 mg/l



of September, 2012.


1AW8Q68G0ZZ __________________________________________________________________






1 pH:n määritys vedestä ja liuoksista CSN ISO 10523 mukaan. ph of water 2 Asetaatin määritys. Tulosten raportointi etikkahappona. Derivatisoinnin jälkeen etikkahapon määritys

headspace GCMS- menetelmää käyttäen. Menetelmä on akreditoittu.


Analysoija1 1 Analysoinnista vastaa ALS Czech Republic, s.r.o., Na Harfê 336/9, 190 00, Praha 9, Tšekki, joka on

akkreditoitu tšekkiläisen akkreditointielimen CAI toimesta (numero L 1163). Laboratoriot sijaitsevat Prahassa (Na Harfê

336/9, 190 00, Praha 9), Ceska Lipassa (Bendlova 1687/7, 470 03 Ceska Lipa) ja Pardubicessa (V Raji 906, 530 02

Pardubice). 2 Analysoinnista vastaa GBA, Flensburger Strasse 15, 25421 Pinneberg, Saksa, joka on akkreditoitu

saksalaisen akkreditointielimen DAR toimesta (numero DAC-P-0040-97-10).


luotettavuustaso on noin 95%. Level of confidence 95 %. Alihankkijoiden mittausepävarmuus on yleensä annettu laajennettuna mittausepävarmuutena, jossa on

käytetty kattavuuskerrointa 2. Laboratoriolta saa lisätietoja pyydettäessä.

Analyysitulokset pätevät ainoastaan analysoiduille näytteille. Lausunto ei kuulu akkreditoinnin piiriin. Tutkimusraportin saa kopioida vain kokonaan. Muussa tapauksessa kopioinnista on saatava lupa

laboratoriolta. Koskien laboratorion vastuita ks. voimassa oleva tuoteluettelo tai www.alsglobal.fi


+ [email protected]

Vain digitaalisesti alekirjoitettu PDF- raportti on alkuperäinen. Kaikki muut printatut versiot ovat kopioita.



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ANNEX 2 FOLLOW-UP FORM FOR TESTING



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CRYOTECH KEMIKAALIEN KOKEILU PASILAN JA ILMALAN RATAPIHOILLA

TALVI 2011 – 2012 TESTING OF CRYOTECH CHEMICALS IN PASILA AND ILMALA RAILWAY YARDS, WINTER 2011 - 2012

Päivä Date

Toimenpideaika

Operation at (h)

Kohde Site

Toimenpide

Activity

Kemikaali tai kemikaaliyhdistel

mä Spread chemical(s)

Määrä g/m2

Amount g/m2

Kokonais-määrä/kerta Total spread amount at one time

Olosuhteet

Conditions

Sateen kesto Rain <1h >1h

Onnistumisen

arviointi Evaluatio

n of success

Kommentit Comments

Note: This is a model form for the collected data.

Documents

TESTING ACETATE-BASED DE-ICING CHEMICALS IN FINLAND …