Air oxidation of d‐limonene (the citrus solvent) creates potent allergens

  title={Air oxidation of d‐limonene (the citrus solvent) creates potent allergens},
  author={Ann-Therese Karlberg and Kerstin Magnusson and Ulrika Nilsson},
  journal={Contact Dermatitis},
Products containing as much as 95% of d‐limonene are used for, e.g., degreasing metal before industrial painting and for cleaning assemblies. Experimental studies on the sensitizing potential of limonene show diverging results. In a previous study, we found that the sensitizing potential of d‐limonene increased with prolonged air exposure. The aim of 1 his study was to make further chemical analyses, to identify compounds formed by air exposure of d‐limonende and to study their allergenic… 

Contact allergy to oxidized d‐limonene among dermatitis patients

An increased UAT of d‐limonene containing allergenic oxidation products in industry where high concentrations are used, as well as in domestic exposure, might result in contact sensitization and dermatitis.

Patch testing with oxidized R‐(+)‐limonene and its hydroperoxide fraction

Clinical support is given to the European classification of R‐(+)‐limonene, containing oxidation products, as a skin sensitizer when using only 1 test preparation for diagnosis of contact allergy to oxidized limonene.

Allergenic activity of an air‐oxidized ethoxylated surfactant

It is shown that the non‐ionic surfactant C12E5 containing 20% oxidation products is a sensitizing mixture that accords with what is observed for other compounds that are unstable when in contact with air, e.g. limonene and linalool, major fragrance terpenes.

Stability of limonene and monitoring of a hydroperoxide in fragranced products

Upon prolonged exposure to air, limonene is prone to oxidation. Hydroperoxides formed upon oxidation are strong skin sensitizers in animal tests and give positive patch tests in human dermatitis

Oxidized citrus oil (R-limonene): a frequent skin sensitizer in Europe.

The high frequency of oxidized limonene allergy provides clinical evidence for the European classification of R-(+)-limonene that contains oxidation products as skin sensitizers.

D-Limonene: Is it a safe, effective alternative to xylene?

Although product safety data sheets mention several adverse effects of exposure to d-limonene, exposure to 76 ppm for 2 hr had no irritative or central nervous system effects in volunteers.

Hydroperoxides in oxidized d-limonene identified as potent contact allergens

Hydroperoxides of d-limonene were shown to be potent contact allergens when studied in guinea-pigs and the cross-reactivity between the epoxide limonene-1,2-oxide, a potent contact allergen, and the hydroperoxide was studied.

Studies on the autoxidation and sensitizing capacity of the fragrance chemical linalool, identifying a linalool hydroperoxide

It is concluded that autoxidation of linalool is essential for its sensitizing potential and in sensitization studies in guinea pigs, linalOOL of high purity gave no reactions, while linalools that had been oxidized for 10 weeks sensitized the animals.

Not only oxidized R‐(+)‐ but also S‐(−)‐limonene is a common cause of contact allergy in dermatitis patients in Europe

Clinical evidence for the importance of oxidation products of limonene in contact allergy is provided, it seems advisable to screen consecutive dermatitis patients with oxidizedLimonene 3% petrolatum, although this patch test material is not yet commercially available.

Analysis of contact allergenic compounds in oxidizedd-limonene

GC-MS with chemical ionization in negative ion mode was shown to be a successful method for the identification and determination of the molecular weight of chemically unstable limonene hydroperoxides and an HPLC method for isolation of individual compounds in auto-oxidizedd-limonene is presented.



Animal experiments on the allergenicity of d-limonene--the citrus solvent.

It is concluded that allergenic compounds are formed from d-limonene upon prolonged air exposure and products containing d- Limonene should therefore be kept in cold storage in closed vessels.

Identification of 15‐Hydroperoxyabietic Acid as a Contact Allergen in Portuguese Colophony

15‐HPA is a main contact allergen in Portuguese gum rosin and its methyl ester was found to be an elicitor when tested in colophony‐sensitized guinea‐pigs.

The influence of limonene on induced delayed hypersensitivity to citral in guinea pigs. II. Label distribution in the skin of 14C-labelled citral.

Results concern the amount of labelled material in soluble compared with insoluble skin protein extracts (SPE) in citral-sensitized animals and the possible role of limonene in alleviating the allergic reaction to citral.

On the Nature of the Eczematogenic Component of Oxidized δ3-carene*

In the experience of both painters and physicians in Sweden, French turpentine has a conspicuously lesser tendency to cause dermatitis, than has Swedish turpentine. Prompted by these observations

The effect of quenching agents on contact urticaria caused by cinnamic aldehyde.

Modulation of immune responses in mice by d-limonene.

Evidence was presented that d-limonene had polyclonal activator action and significant secondary follicle development and prominent lymphoid nodules and aggregates were found in the pancreas and intestinal mucosa, particularly apparent in mice receiving the highest d- Limonene dosage.

HRGC separation of hydroperoxides formed during the photosensitized oxidation of (R)-(+)-limonene

(R)—(+)-Limonene was photooxidized in the presence of Rose Bengal as catalyst. After TLC isolation, the hydroperoxides formed were separated directly by HRGC and analyzed by MS (El; Cl). Each


The value of citrus fruit as a food and as a medicinal agent has been known for many centuries, and within recent years they have been found to be sources of vitamins A, B and C and of comparatively large quantities of calcium.

Studies of the quenching phenomenon in delayed contact hypersensitivity reactions

There was little evidence of quenching of delayed contact hypersensitivity reactions to cinnamic aldehyde or citral in ‘pre‐quenched’ material supplied by a perfume flavour company, and in a similar mixture prepared in this laboratory, in the guinea pig model.