Triazoles in the terrestrial environment - Statsbygg

NGI report no. 20001103-128 February 2002aquateam

Triazoles in the terrestrialenvironmentFinal report20001103-1 28 February 2002Client:Contact person:Contract reference:Oslo Main Airport (OSL)Statsbygg (SB)Norwegian Airforce (LFK)Jarl Øvstedal (OSL)Tone Westby (SB)Gerda Grøndahl (LFK)For the Norwegian Geotechnical InstituteProject Manager:Report prepared by:Reviewed by:Gijs D. BreedveldGijs D. BreedveldRoger Roseth (Jordforsk)Lars Hem (Aquateam)Magnus SparrevikAmy OenPostal address: P.O. Box 3930 Ullevaal Stadion, N-0806 OSLO, NORWAY Telephone: (+47) 22 02 30 00 Postal account: 0814 51 60643Street address: Sognsveien 72, OSLO Telefax: (+47) 22 23 04 48 Bank account: 5096 05 01281Internet: http://www.ngi.no e -mail: ngi@ngi.no Business No. 958 254 318 MVABS EN ISO 9001, Certified by BSI, Registration No. FS 32989

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 3SummaryTo guarantee safety and regularity of air traffic at airports located in coldclimates, large amounts of de-icing chemicals are used on runways andaircrafts prior to take-off. Propylene glycol (PG) is the main constituent used indeicing fluids. Furthermore, additives are added to improve the properties ofdeicing fluids with respect to viscosity (adhesiveness), corrosivity andinflammability. The environmental fate of many of the additives in the deicingagents is poorly understood.Benzotriazole (BT), a corrosion and flame inhibitor, was detected in soil andgroundwater at the former Oslo Airport Fornebu two years after deicingactivities ceased. BT was detected in the groundwater at the new Oslo AirportGardermoen already after the first deicing season (1998-1999). Concentrationsare greatest early in the summer season after the spring snowmelt. No increasein BT groundwater concentrations or off-site migrations have been detectedthus far, including the last measurements/samples taken in the summer of2001.Methyl substituted triazoles or tolytriazoles (MeBT) were found inconcentrations less than 10 % of the BT concentration.BT showed very little sorption in the various soil matrices, only peat andcompost with a high organic carbon content exhibited significant sorption.Sorption could be best described using a Freundlich sorption isotherm. Theseresults indicate a high mobility of BT in soil and groundwater.No proof of microbial degradation of BT under aerobic or anaerobic conditionswas found using inoculumn from both Fornebu and Gardermoen. However,removal of BT was observed under aerobic conditions. This was attributed tovolatilisation, since a similar loss was observed in the abiotic control.Microtox tests of the water samples from Fornebu revealed no acute toxicresponse, however a reduction in nitrification rate was observed. Thenitrification response could not be related directly to the BT concentration inthe samples, although samples with a high BT concentration showed the largestreduction in nitrification rate.BT can be degraded photochemically using UV irradiation. However highradiation doses are required and intermediate products form, which give anegative response in acute toxicity tests. Aniline, Phenazine and an unknowncompound have been detected in treated water samples.The use of BT in many products and applications is widespread. Its mobilenature in the terrestrial ecosystem, the absence of microbial degradation andthe toxicity of the compound has heightened the awareness of using thesechemicals in the environment. However, the absence of information on thelong-term fate of BT warrants further investigations on this group ofcompounds.F:\P\2000\11\20001103\Rap\BTfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 4Contents1 INTRODUCTION.......................................................................................52 ENVIRONMENTAL DATA ON BENZOTRIAZOLE..............................63 OCCURENCE IN SOIL AND GROUNDWATER....................................73.1 Occurence at Fornebu ........................................................................73.2 Occurence at Gardermoen..................................................................94 SORPTION BEHAVIOUR .......................................................................115 DEGRADATION UNDER AEROBIC AND ANAEROBICCONDITIONS...........................................................................................126 TOXICITY OF TRIAZOLES FOR SOIL MICROORGANISMS. ..........137 PHOTO CHEMICAL DEGRADATION..................................................148 CONCLUSIONS AND RECOMMENDATIONS....................................169 DETAILED INFORMATION ..................................................................17REFERENCES ...................................................................................................18Review and reference documentF:\P\2000\11\20001103\Rap\BTfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 51 INTRODUCTIONDeicing chemicals are used at most airports operating in cold climates. Thesafety of air-transport necessitates that runways and aircrafts are kept free ofboth ice and snow. In order to ensure safe take-off and landing, independent ofthe weather conditions, aircraft deicing/antiicing fluids (ADFs) and runwaydeicing chemicals are often required. ADFs are principally based on propyleneglycol (PG) while runway deicers generally are based on potassium acetate,formate or urea. However, the use of PG or ethylene glycol (EG) based deicerson runways has also been reported (Corsi et al., 2001a).During a normal winter at a medium size international airport, the estimatedneed for ADF can vary from 1000-10,000 tons depending on weatherconditions and traffic density (Betts, 1999; Cornell et al., 2000). Most airportsthat use deicing agents for aircrafts have established collection systems torecover concentrated spills. However approximately 20 % of ADFs arediffusively spread along the runways during aircraft take-off and as a result ofsnow clearing (OSL, 2001). Novak and co-workers (2000) report that morethan 60% of the applied ADFs was lost to the surrounding land at a Canadianairport. At Oslo Airport Gardermoen (OSL), a total amount of about 100,000m 3 of stormwater with a concentration range of 20-1600 mg/l PG are generatedeach year, most of which during a short period of snowmelt (S. Moen, 2001,personal communication). At many airports this run-off infiltrates in the subsurfacein an uncontrolled fashion resulting in pollution of ground and surfacewater bodies (Fisher et al., 1995; Corsi et al., 2001a and 2001b). Some airportshave tried to control this run-off and enhance the degradation of deicers in thesoil adjacent to runways to prevent groundwater pollution (Roseth et al., 1998;Breedveld et al., 2001; Switzenbaum et al., 2001).ADFs are typically composed of 50-80 % PG and 20-50 % water. Additives (1-4 %) are used to improve the properties of ADFs with respect to viscosity(adhesiveness), corrosivity and inflammability (Novak et al., 2000). The exactcomposition of the additives may vary between products and is of a proprietarynature (referred to as AdPack). However triazoles in the form of benzotriazoles(BT) or methylbenzotriazoles (MeBT or tolyltriazole), are generally present toreduce the flammability hazard from corrosion of metal components carrying adirect current (Cornell et al., 2000). The concentration of triazoles in undilutedADF has been reported to be approximately 0.05 % (Petersen et al., 1999),while Cornell and co-workers (2000) report values of 0.5 to 0.6 %.Propylene glycol is easily biodegradable and its impact on the soil andgroundwater is well documented (French et al., 2001; Shupack and Anderson,2000; Bakken and Swensen, 1998; Roseth et al., 1998). However, theenvironmental fate and transport of the ADF additives is poorly understood.The detection of benzotriazole in the groundwater below the new Oslo Mainairport at Gardermoen spring 1999 generated an immediate need forf:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 6environmental data on benzotriazoles. In order to fill in the gaps in theavailable data, Jordforsk, Aquateam and NGI initiated an exploratory studyduring 2000 and 2001. The study covered the following topics:• The distribution of triazoles in soil and groundwater at the old Oslo AirportFornebu and the new Oslo Airport Gardermoen.• Sorption behaviour in various soil matrices.• Degradation in groundwater under aerobic and anaerobic conditions.• Toxicity of triazoles for soil microorganisms.Additional research in the field of photochemical degradation by UV-radiationwas initiated to identify treatment options.This report provides an overview over the main findings of this study. Detailson experimental procedures and results are found in the separate reports oneach topic.2 ENVIRONMENTAL DATA ON BENZOTRIAZOLEApart from applications in aircraft deicers, benzotriazole and tolyltriazole arewidely used in cooling fluids, hydraulic fluids, lubricants, polymer stabilizersand in the metal plating industry as brightening agents.BT is a weak organic acid (figure 1a) with a pK a of 8.6 (Andreozzi et al., 1998)and of a weak hydrophobic nature (log K ow = 1.44). Tolyltriazole is usuallyfound as a mixture of two isomers: 4-methylbenzotriazole and 5-methylbenzotriazole(figure 1b) with a pK a of 8.8 and a log K ow > 2 (Cornell et al., 2000).a6574HN123NNb65CH 374HN123NNFig. 1Chemical structures of benzotriazole (a) and tolyltriazole (b).Only limited ecotoxicological data are available, mostly from acute toxicitytests (table 1). A Chronic, 21 day reproduction toxicity tests using Daphniamagna resulted in a no observed effect concentration (NOEC) of 3 mg/l(Sverdrup and Fürst, 1999). Based on these results a predicted no effectconcentration (PNEC) for BT of 0.06 mg/l was calculated (Hem et al., 2000).The compound is classified as “toxic to aquatic organisms and can causelongterm adversary effects in the aquatic environment.”f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 7Table 1Summary of chemical and biological data on benzotriazole availablein literature (Hem et al., 2000).Solubilityg/lBiodegradability20 NotdegradableLogK ow1.440-1.2BacteriaEC 50 mg/lAlgaeEC 50 mg/l>10041 69.9Toxicity dataPelagiccrustacean EC 50mg/lBenticcrustaceanLC 50 mg/kgFishLC 50 mg/l20122 504 130No evidence of microbial degradation of BT or MeBT has been published thusfar (Hem et al., 2000, Gruden et al., 2001). However, a gradual removal hasbeen observed in the presence of peroxidases from horseradish plants andwhite rot fungus Phanerochaete chrysosporium (Wu et al., 1998). Removalfrom the aqueous phase has also been observed in the presence of several otherplants (Castro et al., 2001). However it is unclear whether this removal is aresult of evapotranspiration or transformation/degradation. Rapiddecomposition has been observed by the Fenton reaction and photochemicallyunder the influence of UV irradiation (Wu et al., 1998; Andreozzi et al., 1998).3 OCCURENCE IN SOIL AND GROUNDWATER3.1 Occurence at FornebuOslo’s former airport at Fornebu, which is located on a peninsula in the Oslofjord, was closed in 1998 after 59 years of operation. Redevelopment of the sitefor housing and offices required remediation of contaminated sites. The areasof major concern with respect to contamination by ADFs were the deicing pad,the ADF regeneration plant, the snow disposal site as well as the stormwatercollection/run-off system, which drains towards the fjord (Figure 2). Samplesfrom surface soils, sediments, groundwater and drainage water were collectedapproximately one and two years after airport deicing operations ceased.Table 2BT levels in soil and sediment samples at Fornebu (mg/kg d.w.)Site Depth No. of Mean conc. Min. Max.(m) samplesRunways 0-0.1 20 0.33

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 8BT was detected in low concentrations (0.33 mg/kg d.w. average) in 19 of the20 soil samples taken from the topsoil along the runways (table 2). Elevatedconcentrations (0.66 mg/kg d.w.) were detected at the snow disposal site withno observed difference between the topsoil and 1 meter depth. High concentrationswere observed (13 mg/kg d.w.) in the organic bottom sediments of asmall ditch draining the snow disposal site. BT could also be detected in theupper organic layer of a wetland area receiving the drainage water from thesnow disposal site (0.42 mg/kg d.w.). No BT was detected below 0.1 m depth.In contrast to reports from Northern America (Cancilla et al., 1998; Cornell etal., 2000), BT was the main triazole found at Fornebu, while MeBTs were onlydetected in trace amounts.Fig. 2 Overview over the former airport Fornebu and the sampling sites; A,runways; B, snowdisposal site; C, wetland; D, deicing pad; E,regeneration plant.Groundwater and surface water samples were taken from the snow disposalsite, the drainage ditch, the deicing pad and the ADF regeneration plant. PGf:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 9could be detected in only one of the groundwater samples one year afterdeicing activities ceased at Fornebu. BT was detected in all of the watersamples (table 3). Levels of tolyltriazoles were below 1 µg/l with the exceptionof one sample from the wetland area. The concentration levels varied 3 ordersof magnitude from 1.2 µg/l to 1100 µg/l even within the same location. On thedeicing pad the concentration differences could be related to the soil matrixcomposition. High values were observed in groundwater from the sand andgravel deposits, which were used to backfill, the deicing pad during itsconstruction. Areas with the original peat and clay deposits showed only lowlevels of BT in the groundwater. Groundwater samples were generallyanaerobic with high levels of DOC and a marked sulfidic odour (table 3).Table 3BT and PG levels in groundwater and surface water samples fromFornebuSite BT(µg/l)PG(mg/l)DOC(mg/l)Fe(mg/l)2-SO 4(mg/l)33 4 15.5 - -12 - - - -Snow disposal 8.9 - - - -1.6 - - - -2.7

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 10Deicing pad ANDeicing pad BNRunway WestRunway WestDeicing pad ASFig. 3Overview over the Oslo airport Gardermoen and the sites whichwhere sampled; AN, AS, BN deicing pads.Analysis of the data collected during 1999 and 2000 reveal that highconcentrations of BT are observed in the storm-water system and groundwaterbelow the de-icing platform. Concentrations increase during wintertime,reaching a peak in the spring. Concentrations decrease during late summer andautumn (table 4).f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 11Table 4Maximum and minimum BT concentrations in groundwater samplesfrom Gardermoen spring 2000 to spring 2001.Site BT(µg/l)PG(mg/l)DOC(mg/l)Fe(mg/l)2-SO 4(mg/l)Deicing pad 3.1

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 12Sorption isotherms for the tested soils are presented in figure 4. Almost nosorption was observed in the sandy soils (table 6). The greatest sorption wasobserved for peat and compost, indicating that BT has a high affinity for theorganic carbon in these soil materials. Efficient sorption of BT to organicmaterial was observed both at pH 3 (peat) and pH 7 (compost). At these pHvalues BT is present in an unprotonated form (pKa=8.6) and sorption isbelieved to be of a hydrophobic nature (Jafvert, 1990). The results from thesorption experiments might explain the elevated BT levels in the sediment andwetland samples at Fornebu, which have a high organic carbon content (12-32%). The high mobility of BT in the subsoil and groundwater environment atGardermoen, is consistent with the low organic carbon content in thesesediments (

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 13aerobic conditions resulted in a reduction of benzotriazole in the water phase.However a similar reduction was observed in the control, indicating thatevaporation during aeration might be the major cause for the observed BTremoval. The initial high rate of removal in the aerobic incubations might be aresult of initial sorption to the solid matrix. However BT could not be detectedin the solid phase at the end of the experiments.1,21,0Fornebu - anaerobicGardermoen - anaerobicAbiotic control - aerobicFornebu - aerobicGardermoen - aerobicBenzotriazole (mg/l)0,80,60,40,20,0Fig. 50 1 2 3 4 5Duration (months)Reduction in benzotriazole concentration during aerobic andanaerobic incubation using inoculumn from Gardermoen andFornebu.These results confirm earlier reports in the literature where no biodegradationof BT could be documented. Removal of BT has been observed in experimentsusing phytoremediation (Castro et al., 2001). This might have been caused byevapotranspiration of the plants, since no direct proof of biodegradation waspresented.6 TOXICITY OF TRIAZOLES FOR SOIL MICROORGANISMS.BT has been identified to significantly contribute to the acute toxicity of ADFcontaminated stormwater runoff (Cancilla et al., 1997; Cornell et al., 2000).Therefore additional groundwater samples from the wetland area and thedeicing pad were taken at Fornebu two years after deicing activities ceased.These samples were analysed for their chemical composition as well as acutetoxicity using Microtox as well as a nitrification test. This test is based on areduction in nitrification rates using a mixed culture of ammonium oxidizingbacteria according to ISO standard 9509 (ISO, 1989).f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 14BT could still be detected in all groundwater samples although the levels at thedeicing pad were significantly reduced (table 7). BT was also detected in thestormwater collection/run-off system surrounding the deicing pad, indicatingtransport of BT from the deicing area. Based on these observations and thelocal hydrogeology in the area, the decrease in BT concentration is attributed todilution.Table 7Acute toxicity in groundwater and drainage water samples atFornebu in relation to BT concentrations 2 years after deicingactivities ceased.Site BT(µg/l)DOC(mg/l)Microtox(EC20)Nitrification(%reduction)Wetland3.0 5.3 >100 1438* 4.3 >100 421.2 163 >100 1255 223 >100 43Deicing pad33 132 >100 292.3 85.5 >100 2666** - >100 2035** - >100 26* sample contained in addition 43 µg/l MeBT** samples from drainage system of deicing padNone of the samples showed a toxic response in the Microtox test. Howeverundiluted samples showed a reduction in nitrification activity. The degree ofreduction could not be directly related to the BT concentration in the samples.BT and MeBT have been identified as the compounds most toxic in microbialtest systems (Cornell et al., 2000; Cancilla et al., 1997). However other authorshave reported a complex toxicity response in deicer contaminated runoff,which could not be correlated to a single compound (Corsi et al., 2001b; Novaket al, 2000). Our results support these findings.7 PHOTO CHEMICAL DEGRADATIONPreliminary UV absorbance experiments revealed an absorption maximum at254 nm (figure 6). The UV absorption pattern of benzotriazole changes whenpH exceeds 8, indicating that BT behaves like a weak acid.Based on these results dose-response studies for UV-radiation were performed.A commercial 500 W in line UV lamp with a wavelength of 270 nm ± 30 nmwas used. Varying the hydraulic retention time in the radiation chamberchanged the UV dosage. The initial BT concentration varied from 4.5 to 7.6mg/l and pH was kept at 7 or 8 in the various experiments. Changes in bothchemistry and toxicity were studied.f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 15Relativily high UV dosages were needed to remove BT. pH had a significantimpact on the BT removal efficiency (figure 7). Whereas 65% removal wasobserved at pH 7 and 320 mWs/cm 2 dosage, only 15% removal was observedat pH 8. This is in agreement with results from Andreozzi and co-workers(1998). They indicate that removal efficiency could be improved by reducingthe pH to 5 or lower.120Relative absorbance10080604020pH 3.1pH 5.5pH 7pH 8.1 pH 8.80220 230 240 250 260 270 280 290 300 310 320Wavelength (nm)Fig. 6UV-absorbance of benzotriazole in distilled water at different pHlevels.100reduction of benzotriazole (%)80604020pH 7pH 8Fig. 7010 100 1000 10000UV-dose (mWs/cm 2 )Benzotriazole removal by UV irradiation in potable water atdifferent pH levels.f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 16UV treatment of contaminated groundwater from the deicing platform atFornebu showed a reduction from 81 to 28 µg/l at a dose of 670 mWs/cm2.The removal efficiency is comparable to potable water (65%) however a higherdose was applied. This might have been a consequence of the highconcentration of dissolved organic carbon (DOC > 250 mg/l) in thegroundwater from Fornebu, reducing the UV transmission.Simultaneously with the removal of BT a yellow brown colour was observed inthe aqueous phase and quantified as absorption at 410 nm. The colour intensityincreased with high BT removal, while no colour was observed duringirradiation of BT free water. This indicates the formation of intermediatesduring BT photo chemical degradation.The presence of intermediates was subsequently studied using full-scan GC-MS and toxicity tests. The presence of aniline, phenazine and an unidentifiedcompound was found in the irradiated samples. Highest levels were found inthe sample that received the highest dosage (1000 mWs/cm2). Based on themass-spectrum the unidentified compound might be a condensation product ofpartially degraded BT, containing two aromatic rings.The toxicity test revealed that the toxicity of the aqueous phase decreased moreslowly than the removal of BT, indicating a contribution of the intermediates tothe total toxicity (table 8).Table 8Acute toxicity in BT containing water before and after UVirradiation.Treatment BT(mg/l)Microtox(%)Nitrification(%reduction)EC-20 EC-20 EC-50No-UV 7.6 42 27 68UV 0.87 50 85 1678 CONCLUSIONS AND RECOMMENDATIONSBenzotriazole (BT), a corrosion and flame inhibitor, was detected in soil andgroundwater at the former Oslo Airport Fornebu two years after deicingactivities ceased. BT was detected in the groundwater at the new Oslo AirportGardermoen already after the first deicing season (1998-1999). Concentrationsare greatest early in the summer season after the spring snowmelt. No increasein BT groundwater concentrations or off-site migrations have been detectedthus far, including the last measurements/samples taken in the summer of 2001.Methyl substituted triazoles or tolytriazoles (MeBT) were found inconcentrations less than 10 % of the BT concentration.f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 17BT showed very little sorption in the various soil matrices, only peat andcompost with a high organic carbon content exhibited significant sorption.Sorption could be best described using a Freundlich sorption isotherm. Theseresults indicate a high mobility of BT in soil and groundwater.No proof of microbial degradation of BT under aerobic or anaerobic conditionswas found using inoculumn from both Fornebu and Gardermoen. However,removal of BT was observed under aerobic conditions. This was attributed tovolatilisation, since a similar loss was observed in the abiotic control.Microtox tests of the water samples from Fornebu revealed no acute toxicresponse, however a reduction in nitrification rate was observed. Thenitrification response could not be related directly to the BT concentration inthe samples, although samples with a high BT concentration showed the largestreduction in nitrification rate.BT can be degraded photochemically using UV irradiation. However highradiation doses are required and intermediate products form, which give anegative response in acute toxicity tests. Aniline, Phenazine and an unknowncompound have been detected in treated water samples.The use of BT in many products and applications is widespread. Its mobilenature in the terrestrial ecosystem, the absence of microbial degradation andthe toxicity of the compound has heightened the awareness of using thesechemicals in the environment. However, the absence of information on thelong-term fate of BT warrants further investigations on this group ofcompounds.9 DETAILED INFORMATIONA detailed description of the field and experimental data can be found in thefollowing documents:Sparrevik, M and G.D. Breedveld (2000a)Monitoring data deicing additives, OSL Gardermoen (in Norwegian).Technical note, 15 June 2000, Norwegian Geotechnical Institute, Oslo. 15 p.Sparrevik, M and G.D. Breedveld (2000b)Environmental effects of deicing additives at Fornebu (in Norwegian).Technical note, 3 July 2000, Norwegian Geotechnical Institute, Oslo, 39 p.Roseth, R. and T. Hartnik (2000)Mobility of benzotriazol determined by batch experiments (in Norwegian).Technical note, 5 December 2000, Jordforsk, Ås. 14 p.f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 18Hem, L.J. (2001)Biological degradation of benzotriazole, results of a longterm laboratoryekperiment. Technical note, 17 December 2001, AquateamOslo. 5 p.Hem, L.J., A. Kelley, A. Lundar, T. Hartnik, R. Roseth and G. D. Breedveld(2001)Photochemical degradation of benzotriazole (in Norwegian). Report nr. 01-014, Aquateam, Oslo. 13 p.Norli, R.H. and Fremmersvik, G. (2001)Metabolites of benzotriazole in watersamples after UV irradiation (inNorwegian). Analytical report, 21 August 2001, Jordforsk Lab, Ås. 15 p.REFERENCESAndreozzi, R., Caprio, V., Insola, A. and Longo, G.: 1998, ’Photochemicaldegradation of benzotriazole in aqueous solution’, J. Chem. Technol.Biotechnol. 73, 93-98.Bakken, L. and Swensen, B.: 1998, ‘Deicing chemicals as substrates for themicrobial communities in subsoil’, in T. Nysten and T. Suokko (eds.),Deicing and Dustbinding-Risk to Aquifers, Proceedings of an InternationalSymposium, Helsinki, Finland, 14-18 October 1998, pp. 3-14.Betts, K.S.: 1999, ‘Airport pollution prevention takes off’, Environ. Sci.Technol. 33, 210A-212A.Breedveld, G.D., Børresen, M. and Roseth, R.: 2001, ’Degradation of airportcontaminants in a soil based treatment plant’, Proceedings of the FirstEuropean Bioremediation Conference, Chania, Crete, Greece, 2-5 July2001, pp. 5-8.Cancilla, D. A., Holtkamp, A., Matassa, L. and Fang, X.: 1997, ‘Isolation andcharacterization of Microtox-active component from aircraft deicing/antiicingfluids’, Environ. Toxicol. and Chem. 16, 430-434.Cancilla, D. A., Martinez, J. and Van Agglen, G. C.: 1998, ‘Detection ofAircraft Deicing/antiicing fluid Additives in a perched water monitoringwell at an International Airport’, Environ. Sci. Technol. 32, 3834-3835.Castro, S., Davis, L.C. and Erickson, L.E.: 2001, ’Plant-enhanced remediationof glycol-based aircraft deicing fluids’,Practice Periodical of Hazardous,Toxic, and Radioactive Waste Management, 5, 141-152.Cornell, J. S., Pillard, D. A. and Hernandez, M. T.: 2000, ‘Comparativemeasures of the toxicity of component chemicals in aircraft deicing fluids’,Environ. Toxicol. and Chem., 19, 1465-1472Corsi, S.R., Hall, D.W. and Geis, S.W.: 2001a, ’Aircraft and runway deicers atgeneral Mitchell international airport, Milwaukee, Wisconsin, USA. 1.Biocehmical oxygen demand and dissolved oxygen in receiving streams’,Environ. Toxicol. and Chem., 20, 1474-1482.f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 19Corsi, S.R., Hall, D.W. and Geis, S.W.: 2001b, ’Aircraft and runway deicers atgeneral Mitchell international airport, Milwaukee, Wisconsin, USA. 2.Toxicity of aircraft and runway deicers’, Environ. Toxicol. and Chem., 20,1483-1490.Fisher, D.J., Knott, M.H., Turley, S.D., Turley, B.S., Yonkos, L.T. and Ziegler,G.P.: 1995, ’The acute whole effluent toxicity of storm water from andinternational airport’, Environ. Toxicol. and Chem., 14, 1103-1111.French, H.K., van der Zee, S.E.A.T.M. and Leijnse, A.: 2001, ’Transport anddegradation of propyleneglycol and potassium acetate in the unsaturatedzone’, J. Contam. Hydrol. 49, 23-48.Gruden, C.L., Dow, S.M. and Hernandez, M.T.: 2001, ’Fate and toxicity ofaircraft deicing fluid additives through anaerobic digestion’, Water Environ.Res., 73, 72-79.Hem, L. J., Weideborg M. and Schram E.: 2000, ‘Degradation and toxicity ofadditives to de-icing fluids; the effect of discharge of such fluids tomunicipal wastewater treatment plants’, in Proceedings WEF and PurdueUniversity Industrial Wastes Technical Conference, St. Louis, USA, 21-24May 2000, 15 pp.ISO: 1989, ’Water quality -- Method for assessing the inhibition of nitrificationof activated sludge micro-organisms by chemicals and waste waters’, ISO9509, International Organization for Standardization, Geneva, Switzerland,6 pp.Jafvert, C.T.: 1990, ’Sorption of organic acid compounds to sediments: Initialmodel development’, Environ. Sci. Technol. 9, 1259-1268.Novak, L.J., Holtze, K., Kent, R.A., Jefferson, C. and Anderson, D.: 2000,’Acute toxicity of storm water associated with de-icing/anti-icing activitiesat Canadian airports’, Environ. Toxicol. and Chem., 19, 1846-1855.OECD: 1981, ‘Adsorption-desorption using a batch equilibrium model’. OECDGuideline for the Testing of Chemicals no.106, OECD, Paris, France, 23 pp.OSL: 2001, Environmetal Report 2000 (in Norwegian), Oslo Lufthavn AS,Gardermoen, Norway, 30 pp.Petersen, G.I., Tørslev, J. And Madsen, T.: 1999, ’Copenhagen airport,environmental evaluation of benzotriazole and tolyltriazole (in Danish)’,Technical report, VKI, Hørsholm, Denmark, 10 pp.Roseth, R., Bjørnstad, H., Kraft, P. and Warner, B.: 1998, ‘Airport stormwatertreatment in constructed soil filters – a comparative study of aircraftdeicers’, in T. Nysten and T. Suokko (eds.), Deicing and Dustbinding-Riskto Aquifers, Proceedings of an International Symposium, Helsinki, Finland,14-18 October 1998, pp. 155-165.Schwarzenbach, R.P., Gschwend, P.M. and Imboden, D.M.: 1993,Environmental Organic Chemistry, John Wiley & Sons, New York, 681 pp.Shupack, D.P. and Anderson, T.A.: 2000, ‘Mineralization of propylene glycolin root zone soil’, Water, Air, and Soil Pollut. 118, 53-64.Sverdrup, L.E. and Fürst, C.S.: 1999, ‘Chronic toxicity test results withDaphnia magna for the test substance S4’, Technical report, KMLab/Aquateam, Oslo, Norway.f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Triazoles in the terrestrial environment Report No.: 20001103-1Date: 2002-02-28Rev.:Final reportRev. date:Page: 20Switzenbaum, M.S., Veltman, S., Mericas, D., Wagoner, B. And Schoenberg,T.: 2001,’ Best management practices for airport deicing stormwater’,Chemosphere, 43, 1051-1062.Wu, X., Chou, N., Lupher, D. And Davis, L. C.: 1998, ‘Benzotriazoles: toxicityand degradation’, in Proceedings of the 13 th annual Conference onHazardous Waste Research, Kansas State University Manhattan, Kansas,USA, 1998, pp. 374-384.f:\p\2000\11\20001103\rap\btfinalreport.docGBr/wut

Kontroll- og referanseside/Review and reference pageOppdragsgiver/ClientOslo Main Airport (OSL), Statsbygg (SB), Norwegian Airforce (LFK)Dokument nr/Document No.20001103-1Kontraktsreferanse/Contract referenceDokumenttittel/Document titleTriazoles in the terrestrial environmentProsjektleder/Project ManagerGijs D. BreedveldUtarbeidet av/Prepared byGijs D. Breedveld, Roger Roseth (Jordforsk), Lars Hem (Aquateam)Emneord/Keywordssoil groundwater contamination, deicers, triazole, sorption, degradation, toxicityDato/Date28 February 2002Distribusjon/Distribution Fri/Unlimited Begrenset/Limited Ingen/NoneLand, fylke/Country, CountyHavområde/Offshore areaKommune/MunicipalityFeltnavn/Field nameSted/LocationSted/LocationKartblad/MapFelt, blokknr./Field, Block No.UTM-koordinater/UTM-coordinatesKvalitetssikring i henhold til/Quality assurance according toNS-EN ISO9001Kon-Dokument/Document Revisjon 1/Revision 1 Revisjon 2/Revision 2trollertav/ReviewedbyAOAOAOKontrolltype/Type of reviewHelhetsvurdering/GeneralEvaluation *Språk/StyleTeknisk/Technical- Skjønn/Intelligence- Total/Extensive- Tverrfaglig/InterdisciplinaryKontrollert/Reviewed Kontrollert/Reviewed Kontrollert/ReviewedDato/Date Sign. Dato/Date Sign. Dato/Date Sign.WUTGBrJSUtforming/LayoutSlutt/FinalKopiering/Copy quality* Gjennomlesning av hele rapporten og skjønnsmessig vurdering av innhold og presentasjonsform/On the basis of an overall evaluation of the report, its technical content and form of presentationDokument godkjent for utsendelse/Document approved for releaseDato/DateSign.