Hydroperoxider – så kan eteriska oljor ge kontakteksem

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Så bryts vanliga doftämnen ner till hudirriterade ämnen

Ett av världens vanligaste doftämnen är limonen, som utvinns ur citrusfrukternas skal och linalool, som bland annat finns i lavendelolja. De används som doftsättare i en stor andel parfymer, kosmetika, hygienprodukter och rengöringsmedel. Limonen används även som miljövänligt lösnings- och avfettningsmedel inom industrin. De kan framställas syntetiskt men ingår framförallt som helt naturliga komponenter i vissa eteriska oljor. Limonen och linalool är två av de 26 allergiframkallande doftämnena som enligt lag måste anges i ingredienslistan på kosmetika och hygienprodukter eftersom de är kända för att kunna orsaka hudalleriger och kontakteksem. Det är inte doftämnena i sig som är allergena, utan den nedbrytningsprodukt som bildas när de oxiderar i kontakt med luften. Då bildas de kraftigt allergiframkallande hydroperoxiderna. Något som forskare nu har upptäckt sker snabbare än vad man tidigare trott. Många av de undersökta eteriska oljorna hade redan bildat hydroperoxider när de kom från leverantören.

Parfymallerier ökar kraftigt

Oxiderande doftämnena är snudd på omöjliga att undvika, eftersom de är så vanligt förekommande i många av våra vardagsprodukter. De finns i allt från diskmedel, schampo, deodorant, tvättmedel, tandkräm och ekologisk babylotion. Därför är också doftallergi en form av allergi som ökar kraftigt. Idag tror man att fem till sju procent av alla med allergiska kontakteksem har utvecklat en allergi mot just de oxiderande doftämnena.

Ny anlysmetod avslöjar hydroperoxider i konsumentprodukter

Fram tills helt nyligen har man inte kunnat mäta de flykiga och instabila hydroperoxiderna. De analysmetoder man har haft har inte varit tillräckligt känsliga. Parfymindustrin har i princip använt metoder från 1800-talet, vilket gjort att man har missat de här svårupptäckta ämnena. Men nu har man på institutionen för Kemi och molekylärbiologi vid Göteborgs universitet utvecklat en helt ny analysmetod som gör att det faktiskt går att undersöka hydroperoxider i olika konsumentprodukter.

– Med hjälp av masspektrometri slår man sönder ämnena så att de bilar små fragment och det är första gången som det finns en metod att hitta de här enskilda specifika hydroperoxiderna i små mängder och i komplexa blandningar, förklarar Johanna Rudbäck som är doktorand vid Göteborgs universitet. Johanna Rudbäck disputerat i höstas med avhandlingen ”Allergenic Oxidation Products from Fragrance Terpenes. Chemical Analysis and Determination of Sensitizing Potency”.

Eteriska oljor oxiderade redan hos leverantören

Ann-Therese Karlberg, professor i dermatokemi och hudallergi på Göteborgs universitet menar att det bara behövs små mängder av hydroperoxider för att trigga en allergi och ett eksemen hos en person som redan har utvecklat en överkänslighet. När man använde den nya analysmetoden för att studera eteriska oljor från lavendel och apelsinskal upptäckte man att de oxiderade fortare än man tidigare hade trott.

– Vi såg att det bildats hydroperoxider redan när vi fick oljorna från leverantören. Det förvånande oss, säger Johanna Rudbäck.

Naturligt eller syntetiskt – lika allergiframkallande

Man hör ofta kommentaren att naturligt framställda doftämnen inte skulle vara lika allergiframkallande som syntetiska. Att det skulle finnas naturliga antioxidanter i eteriska oljor som skyddar dem från att oxidera. Något som tyvärr alltså inte verkar stämma. Professor Ann-Therese Karlberg förklarar:

" ...Generellt sett gäller att de doftämnen som framställs på syntetisk väg även ingår i eteriska oljor. Detta gäller tex linalool från lavendelolja. Vi har kunnat konstatera att linalool oxideras på samma sätt och lika fort i den naturliga eteriska oljan som när det är framställt på syntetisk väg. Det finns ingenting i dag som visar att inte hydroperoxider kan ingå i parfymerade kemisk-tekniska produkter (konsumentprodukter)...”

Och även fast man inte har analyserat färdiga konsumentprodukter (som har doftsatts med eteriska oljor) utan bara de eteriska oljorna så menar Ann-Therese Karlberg  att de allergiframkallande hydroperoxiderna helt enkelt följer med in i slutprodukten.

”... När det gäller limonen använder man den eteriska oljan direkt som doftämne i de parfymerade produkterna eftersom den består till mer än 90% av limonen. Vi har funnit att sådan olja innehåller hydroperoxider när den kommer från leverantören.  Därför kommer även hydroperoxiderna att ingå i den färdiga produkten...” 

Eteriska oljor och parfymerade produkter får inte bli gamla

Om man är orolig för att utveckla en kontaktallergi bör man vara uppmärksam på innehållsförteckningarna och undvika dessa ämnen menar Ann-Therese Karlberg. Den som ändå vill köpa parfymerade produkter och eteriska oljor bör vara extra observant på datum och hållbarhet.

– Mitt råd är att man ska vara observant på innehållsförteckningarna av till exempel sina deodoranter och andra kosmetiska produkter. Sen ska man inte ha dem för länge utan man ska köpa nytt.

Hydroperoxidernas allergena mekanismer nu kartlagda

En annan forskare som studerat hydroperoxider är Staffan Johansson vid Institutionen för kemi vid Göteborgs universitet. Han har upptäckt och kartlagt de mekanismer som styr hur allergiframkallande de olika hydroperoxiderna är från den citrusdoftande limonen. För ett eksem ska kunna bildas krävs att ett ämne binder sig till proteiner i huden. När det gäller hydroperoxider tror man att det sker med sk radikaler. För hydroperoxiderna bryts nämligen i sin tur ner till de kraftigt reaktiva molekyler som kallas radikaler. Vissa av dem är sk syrecentrerade radikaler (dvs radikaler som binder sig till en syreatom) och de har visat sig ge en kraftigare reaktion i huden. Med andra ord så har de hydroperoxider som bildar en stor andel syrecentrerade radikaler visat sig vara extra starka kontaktallergener.

Åtgärdsprogram för ökad säkerhet

För att öka säkerheten kring parfymkomponenter har parfymindustrin startat ett åtgärdsprogram. Här kan de nya kunskapen om hydroperoxider komma att bli en viktig pusselbit. Det menar Vd Olof Holmer, på kemisk-tekniska leverantörsförbundet (KTF) som välkomnar de nya forskningsrönen. Det låter fantastiskt ifall parfymindustrin äntligen kunde hitta en lösning på problemet med de oxiderande doftämnena. Kanske kan man utveckla metoder som skyddar de här härligt väldoftande ämnena från att oxidera och blida skadliga hydroperoxider? Tills det sker så sparar jag parfymen till fest, undviker eteriska oljor och väljer oparfymerat så ofta jag kan! 

 

In english

Common fragrance compounds like limonene and linalool oxidize upon contact with air, forming hydroperoxides which are strong skin sensitizers. Until recently hydroperoxides have generally been difficult to determine. A group of scientists at the University of Gothenburg has now developed new analytical methods and chemical analyses for detection of hydroperoxides in complex mixtures. For the first time utilizing a mass spectrometry. Limone and linalool are components in essential oils like lemon and lavender. It has often been stated that natural occuring antioxidants in the oils are protecing them from oxidation. Unfortunately this is not the case. In the study ”Allergenic Oxidation Products from Fragrance Terpenes. Chemical Analysis and Determination of Sensitizing Potency”, by Johanna Rudbäck the presence of hydroperoxides where established in the essential oils alredy upon delivery from the suppliers.


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Kommentarer

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Mona,

Mycket intressant (som alltid Mitte)! Detta med hydroperoxider hade helt undgått mej, alltså att det egentligen inte är själva et. oljan som är problemet utan vad som händer när oljan oxiderar. Hade ju verkligen varit fantastiskt om forskarna kunde hitta en lösning! Om jag fattat det hela rätt så uppstår den allergiska reaktionen i kontakt med huden. Är det kanske då ok att använda aromalampa eller hemmagjort rumsspray?

Jag använder en hudkräm som känns skräddarsydd för min hud förutom att den innehåller et. olja. Är överkänslig mot limone och geraniol men enligt INCI innehåller krämen inga doftämnen alls. Dumt att använda krämen ändå? Har funderat på att försöka efterlikna krämen och göra en egen utan parfym. Men då kommer man till problemet med ok konserveringsmedel (vill helst ha kräm). Svår avvägning vilket som skadar mest, parfym eller parabener liksom… Vet du Mitte hur det är med hydrolater som sägs vara en restprodukt vid framställningen av et oljor, är det samma risk för allergi? Annars kunde man ju få lite doft genom nåt blomvatten...

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Mitte,

Hej Mona, tusen tack för smart och bra kommentar (som alltid! :))

Skulle också tolka det som att det är ok att använda aromalampa och rumspray givet att den irriterande/allergiska reaktionen uppstår i huden. Samtidigt har man ju hört om riktiga parfymallergiker som får hösnuva bara de är i samma rum som någon med parfym. Fast det kanske handlar om någon helt annan typ av överkänslighet?

Vad gäller den parfymerade krämen du skriver om så står det alltså "parfum" på innehållsförteckningen? Eller står det "fragrance"? För enligt lagstifningen inom EU så måste alla kosmetiska produkter som innehåller några av de 26 särskilt allergena doftämnena (bland annat limone och geraniol) innehållsdeklarera dessa. Övriga doftämnen går bra att samla under namnet parfum (oavsett om de är syntetiska eller naturliga). Det anses vara en affärshemlighet vilka exakta doftblandningar  man har använt så därför behöver man i övrigt inte skriva ut detta i detalj. Vilket även är skälet till varför man inom USA bara behöver skriva ut "Fragrance", även fast de kanske innehåller någon av de 26 allergena doftämnena (dvs står det fragrance på din produkt kan den mycket väl innehålla just de doftämnen du är allergisk mot). I USA har man alltså en ur konsutmentsynvikel svagare lagstiftning.

Här har jag listat de 26 särskilt allergena doftämnena:

http://beautycomesclean.se/blogg/201206/26-allergiframkallande-parfymamn...

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Mona,

Supertack Mitte för ditt engagerade svar! :) Så knepigt detta med parfym i INCi var nu då! Krämen jag använder är Sante Nattcreme Goji torr hy och nu är jag fräck som tar mycket plats med att pasta in innehållet: ”INCI: Aqua (Water), Glycine Soja (Soybean) Oil*, Isoamyl Laurate, Cyperus Esculentus Root Oil*, Theobroma Cacao (Cocoa) Seed Butter*, Cetyl Alcohol, Cocoglycerides, Olea Europaea (Olive) Fruit Oil*, Prunus Amygdalus Dulcis (Sweet Almond) Oil*, Cetearyl Olivate, Glycerin, Butyrospermum Parkii (Sheabutter)*, Parfum (Essential Oils), Sorbitan Olivate, Sorbitol, Xanthan Gum, Simmondsia Chinensis (Jojoba) Seed Oil*, Rhus Verniciflua Peel Wax, Sodium PCA, Sodium Levulinate, Aloe Barbadensis Leaf Juice*, Lycium Barbarum Fruit Extract*, Passiflora Incarnata Extract*, Sodium Anisate, Sodium Lactate, Lactic Acid, Tocopherol, Helianthus Annuus (Sunflower) Seed Oil*”.
Krämen luktar jättegott (i min gottegrisnäsa iaf ;)), typ marängsviss! Är nog gojibären, passionsblomman och kakaosmöret som luktar också men det står alltså parfum (rätt högt upp i listan tyvärr). Det borde väl betyda att de doftämnen jag är känslig för inte finns i? Fast helst skulle den ju inte innehålla parfym alls…

Bild för Mitte
Mitte,

Hej igen Mona, jag antar att det delvis kan bero på hur noggranna tillverkaren är med att följa de regler som finns (med att ev skriva ut de 26 mest allergena doftämnena). Du kanske kunde mejla dem och fråga vilka eteriska oljor de tillsatt och då även skriva att du är allergisk mot limone och geraniol. Då borde du väl rimligen kunna få ett svar? Låter för övrigt som en riktigt härlig doft, hoppas du kan använda den! :)

Bild för Mona
Mona,

Hej och tack igen Mitte! Bra idé, leka lite detektiv...Får isf hoppas de kan engelska någorlunda (tyskt företag). Och sen var det ju det där med affärshemligheter...

Bild för Lisa
Lisa,

Vilket bra och informativt inlägg! Måste nog försöka hitta ett doftfritt alternativ till barnen trots allt. Vi använder weleda här hemma men de är ju definitivt inte doftfria. Gillar dock deras produkter men det måste ju gå att hitta något likvärdigt.

Bild för Mitte
Mitte,

Hej Lisa, jag gillar också Weleda och tycker precis som du att de är trist att de inte är doftfria. Kan kanske få tipsa om Estelle & Thild som har parfymfria produkter för barn. Lycka till och hör gärna av dig om du hittar något bra alternativ! :)

Bild för Ellinor

Det hade varit mycket intressant att veta exakt vilka leverantörer de använt sig av. Oxidering kan tyvärr hända vid industriell storskalig (billig) tillverkning av eteriska oljor. Då används mycket stora volymer av råvaran (som ofta är av sämre kvalitet), under mycket högt tryck och alldeles för hög värme för att få ut så mycket eteriska olja som möjligt. Då är tyvärr den eteriska oljan redan oxiderad och förstörd vid tillverkningen. Vill bara belysa att detta inte förekommer vid hantverksmässig framställning av eteriska oljor av hög kvalitet då man noggrant kontrollerar värme och tryck för att detta inte ska hända. Så kvaliteten är verkligen enorm mellan olika framställare.

Kan även tipsa om att endast använda professionella doftlampor, de är designade så att temperaturen aldrig överstiger 55 grader, annars finns risken att oljan börjar koka eller i värsta fall brinna som lätt kan hända med billigare lampor.

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