Effekten af pH på dannelsen af biprodukter
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Kamilla Hansen fremlagde resultater fra forsøg lavet på DTU Miljø. Effekten af pH i badevandet på dannelsen af desinfektionsbiprodukter var undersøgt for klorering af kropsvæske analog og partikler opsamlet på tromlefilter. Ved at sænke pH fra 7,5 til 6,5 blev der observeret en reduceret trihalometan dannelsen i begge tilfælde, mens haloacetonitril og trikloramin dannelsen steg. Haloeddikesyrerne var uændret ved klorering af kropsvæske analog og faldt ved partikelforsøget med pH. For at evaluere betydningen af ændringerne i dannelse af de analyserede biprodukter var den samlede toksicitet beregnet: Toksiciteten blev næsten fordoblet ved pH 6,5 i forhold til pH 7,5 og tredoblet ved pH 6,0. Konklusionerne var at det er tvivlsomt om man får en bedre badevandskvalitet ved at sænke pH selvom THM koncentrationerne falder. Undersøgelsen viser dermed at THM ikke er egnet som testparameter ved evaluering af ændringer i drift af svømmebade eller i vandbehandlingen.
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Effekten af pH på dannelsen af biprodukter
- 1. Effekten af pH på dannelsen af biprodukter - Måler vi de relevante biprodukter? Kamilla Hansen og Henrik R. Andersen
- 2. Klorering Klor HOCl OCl - + H + pKa = 7.54 @ 25°C pH i svømmebade skal være mellem 7 og 8 HOCl bedst til at disinficere
- 3. Biprodukter Klor + Snavs Biprodukter Trihalometan(THM) Haloeddikesyre(HAA) Trikloramin(NCl 3 ) Haloacetonitril(HAN)
- 4. Lavkloreringsforsøg Gladsaxe Der blev lavet forsøg med lavklorering i et varmtvandsbassin i Gladsaxe svømmehal. Sammenligne normaldrift og forsøgsdrift Der blev målt THM, AOX og bakterieniveau
- 5. Lavkloreringsforsøg Gladsaxe Disinfikationskraften bevares ved samtidig sænkning af pH og klordosis pH Frit klor Normal 7.3 1.5 mg/L Forsøgsdrift 6.7 0.4 mg/L
- 6. Lavkloreringsforsøg Gladsaxe Hovedsagelig chloroform Lav klor og pH lav THM koncentration (ca 20 µg/L) Normal klor og pH THM koncentration ca 45 µg/L
- 7. Konklusioner fra Gladsaxe forsøget ” Sammenfattende kan det konkluderes, at det synes muligt at opnå betydelige forbedringer i vandkvalitet – og dermed også forbedret indeklima – i svømmebadsanlæg ved at drive svømmebadene ved lavere indhold af frit klor.” ” Den hygiejniske kvalitet af bassinvandet var gennem forsøgsperioden uændret god ved de nye driftsforhold med frit klor 0,4 mg/l og pH omkring 6,7.” ” Indholdet af THM steg fra et niveau omkring 15-25 μg/l til et niveau omkring 40-50 μg/l, når frit klor steg fra 0,4 mg/l til 1,5 mg/l. Hovedparten af THM fandtes som forventet som kloroform.” Kristensen et al., Forsøgsdrift af varmtvandsbassin I Gladsaxe svømmehal ved lavt indhold af frit klor og reduceret. DHI Danmark, Juni 2007
- 8. Pas på – hvis vi sænker pH så… Hvad med trikloramin (NCl 3 ) – Den vil stige og er oprindelig årsagen til reglen pH > 7 i svømmebade Indikation på stigning af haloeddikesyrer og haloacetonitriler i litteraturen Bliver det sundere? Dvs. < toksisk
- 9. Hvilke biprodukter? Biprodukter Trihalometan Haloeddikesyre Trikloramin Klor + Snavs Haloacetonitril pH klor dosis
- 10. Svømmebad Partikler: Kropsvæsker mm.: Snot Sved Urin Creme Shampoo Hår Hud …
- 11. Kropsvæske analog Hovedkomponenterne i sved og urin (Judd & Bullock, Chemosphere, vol 51, 2003): Ammonium chloride NH 4 Cl Urea NH 2 CONH 2 Creatinin C 4 H 7 N 3 O Histidin C 6 H 9 N 3 O 2 Hippursyre C 9 H 9 NO 3 Urinsyre C 5 H 4 N 4 O 3 Citronsyre C 6 H 8 O 7
- 12. Partikler fra tromlefilter &;10µ
- 13. Forsøgsdesign 48 timer ved 25°C Målinger: pH og klor Trihalomethan (THM) Haloeddikesyre (HAA) Haloacetonitril (HAN) Trichloramin (NCl 3 ) Kropsvæske / Partikler Klor Buffer
- 14. Forsøgsdesign Enten total klor eller disinfikationskraft konstant. Disinfikationskraften falder Total klor stiger
- 15. Effekt på dannelsen af biprodukter ved sænkning fra pH 7.5 til pH 6.5 * Ikke dannet, men kun analyseret ved pH 6 Dvs. trikloramin dannes tilsyneladende ikke på filtrene Kropsvæske Partikel Trihalometan Haloeddikesyre – Haloacetonitril NCl 3 *
- 16. Toksicitet Toksiciteten af de forskellige grupper Haloacetonitriler(HAN)>Haloeddikesyrer (HAA)>Trihalomethaner (THM) Toksiciteten kan beregnes for en vandprøve således: EC 50 -værdierne er fra artikel (Plewa et al. 2008) Plewa et al., Comparative Mammalian Cell Toxicity of N-DBPs and C-DBPs. In Disinfection By-Products in Drinking Water: Occurrence, Formation, Helth Effects, and Control , American Chemical Society: Washington, DC, 2008.
- 17. Beregnet toksicitet Toksiciteten af det klorede vand med kropsvæske halveres ved ændring af pH fra 6 til 7. Partiklerne giver mere toksitet ved pH lavere end 7.5. pH afhængighed ligner den for haloacetonitril
- 18. Konklusion Dannelsen af disinfikationsbiprodukter er afhængig af pH -Specielt trikloramin (NCl 3 ) og haloacetonitriler (HANs) Den beregnede toksicitet af vandet stiger ved lavere pH HAN’erne bidrager mest til toksiciteten. THM kan muligvis bruges som indikator for badebelastning men er ikke brugbar som testparameter ved evaluering af ændringer i drift eller vandbehandlingen.
- 19. Tak for opmærksomheden Tak til mine vejledere: Hans-Jørge Albrechtsen, Hans Mosbæk og Henrik Andersen Samt tak til Sarah Willach for hjælp i laboratoriet