Disposable optical sensor for Al(III) ions determination by coupled colorimetric solid-phase extraction-reflectance spectroscopy in leachates from cookware, antacids and hygienic care products.

A disposable and miniaturised optical sensor based on colorimetric solid-phase extraction has been designed using poly(styrene-divinylbenzene) membrane disks modified with the colorimetric reagent pyridoxal salicyloylhydrazone to determine the aluminium concentration in aqueous solutions. The extraction of Al(III) ions by the reagent immobilised onto a disk allows the quantification directly on the adsorbent surface by a miniature portable reflectance spectrometer with an optical fibre at 434 nm. The optimisation of the sensing system was carried out by a fractional factorial design 33-1 considering the extraction pH, amount of ligand immobilised onto the disk and time of immobilisation as experimental factors. The linear dynamic range of the sensor response ranged from 0.18 to 2 mg L-1 Al(III) with a detection limit of 0.18 mg L-1 (n = 10), being the precision of 6.3% for 1 mg L-1 Al(III) (n = 10, confidence level of 95%). The proposed method was successfully applied to the analysis of aluminium in leachates from cookware, antacids and hygienic care products, as contribution to the concern about aluminium as a known systemic toxicant at high doses.

Health risk assessment of dermal and inhalation exposure to deodorants in Korea.

In Korea, humidifiers that include biocidal ingredients have caused serious lung injuries and deaths. After these incidents, public concern regarding the use of chemicals in products (i.e., chemical phobia) increased. Frequent health risk assessments and stringent management of consumer products are, therefore, of paramount importance to reduce these serious occurrences. In this study, the irritative and respiratory health effects of deodorants were assessed in relation to dermal and inhalation exposure. In total, 64 deodorants were divided into 5 groups by application type, and health risk assessments were conducted on each group. In total, 26 fragrance ingredients and 27 biocidal ingredients were analyzed and assessed according to their risk to human health. Exposure assessment was performed in two steps. In the tiered 1 assessment (screening), the 95th exposure factor values were used to estimate exposure to assume the worst-case scenario. The maximum concentration in the deodorants was used without considering the application type. In the tiered 2 assessment (detail assessment), the 75th exposure factor values were used to estimate the assumed reasonable exposure to ingredients. In these assessments, the maximum concentration used in the exposure models was determined by the product purpose and application type. The values input into the exposure algorithms were developed via the exposure route. Of the selected fragrance and biocidal active ingredients, 18 fragrance and 13 biocidal ingredients were detected in the deodorants that were assessed. From the results of the tiered 1 assessment, it was necessary for tiered 2 risk assessments to be conducted for 6 ingredients for the inhalation route, and 13 ingredients for the dermal route. The inhalation margin of exposure of ingredients in deodorants of gel/trigger/spray types for home/car and fabric/air usage was above the target margin of exposure. The health risk of 6 evaluated ingredients was relatively low for the inhalation route of exposure. This study showed that the assessed ingredients have no health risks at their maximum concentrations in deodorants. The approach discussed in this study should be used to establish improved guidelines for specific ingredients in consumer products, and for setting limits for newly developed raw materials that may pose dermal and inhalation hazard.

Comparison and analysis of several wet scrubbing solutions to remove methyl mercaptan.

Wet scrubbing is regarded as an effective method to remove hydrophobic organic odorants. The focus of wet scrubbing is to choose an appropriate scrubbing liquid. In this study, methyl mercaptan (CH3SH) was selected as a representative hydrophobic organic odorant for treatment by wet scrubbing using several types of scrubbing solution: ethanol (C2H5OH), lead acetate ((CH3COO)2Pb), sodium hypochlorite (NaClO), and sodium hydroxide (NaOH). A comparative analysis of the treatment efficiency, operation cost, and environmental impact was conducted. Results of the technical and economic comparison indicate that the C2H5OH solution is the best choice of scrubbing solution among those tested. These findings serve as a reference for engineering design and operation for the removal of hydrophobic organic odorants.

Deodorizing Substance in Black Cumin (Nigella sativa L.) Seed Oil.

A deodorizing substance in black cumin (Nigella sativa L.), a spice for curry and vegetable foods in Southwest Asia, was examined. The essential oil prepared from the seeds of this plant exhibited strong deodorizing activity against methyl mercaptan, which is a main factor in oral malodor. After purification with silica gel column chromatography, the active substance in black cumin seed oil was identified as thymoquinone. This monoterpenic quinone functions as the main deodorizing substance in this oil against methyl mercaptan. Metabolite analysis suggested that the deodorizing activity may be generated by the addition of a reactive quinone molecule to methyl mercaptan. In the present study, the menthane-type quinone and phenol derivatives exhibited deodorizing activities via this mechanism.

Analysis of cocaine and metabolites in hair: validation and application of measurement of hydroxycocaine metabolites as evidence of cocaine ingestion.

An LC/MS/MS method to identify and quantitate in hair the minor metabolites of cocaine-meta-, para-, and ortho-hydroxy cocaine-was developed and validated. Analysis was performed on a triple quadrupole ABSciex API 3000 MS equipped with an atmospheric pressure ionization source via an IonSpray (ESI). For LC, a series 200 micro binary pump with a Perkin Elmer Model 200 autosampler was used. The limit of detection (LOD) and limit of quantification (LOQ) were 0.02 ng/10 mg hair, with linearity from 0.02 to 10 ng/10 mg hair. Concentrations of the para isomer in extensively washed hair samples were in the range of 1-2 % of the cocaine in the sample, while the concentrations of the ortho form were considerably less. The method was used to analyze large numbers of samples from two populations: workplace and criminal justice. In vitro experiments to determine if deodorants or peroxide-containing cosmetic treatments could result in the presence of these metabolites in hair showed that this does not occur with extensively washed hair. Presence of hydroxycocaines, when detected after aggressive washing of the hair samples, provides a valuable additional indicator of ingestion of cocaine rather than mere environmental exposure.

Effect of deodorant and antiperspirant use and presence or absence of axillary hair on absorption of testosterone 2% solution applied to men's axillae.

INTRODUCTION: Testosterone 2% solution is applied to axillae and is indicated for testosterone replacement therapy in males deficient in endogenous testosterone. AIM: This open-label crossover study evaluated the effect of deodorant/antiperspirant use and presence or absence of axillary hair on absorption of testosterone solution. METHODS: Healthy males (N = 30; ≥50 years of age with baseline testosterone <400 ng/dL) were randomized to one of four treatment sequences involving six treatments. Each treatment consisted of one 1.5-mL dose of testosterone 2% solution (30 mg of testosterone) applied to each axilla. Axillae were unshaved or shaved, and were untreated or pretreated with deodorant/antiperspirant. MAIN OUTCOME MEASURES: Blood samples were taken over 72 hours after each dose for measuring serum testosterone concentrations. RESULTS: Profiles of mean testosterone concentrations were similar across treatments. For all treatments, area under the concentration-time curve through 24 hours (AUC[0-24] ) and 72 hours (AUC[0-72] ), and maximum total testosterone concentration (Cmax ) were similar except for 15% lower Cmax when treatment was applied after deodorant/antiperspirant to shaved vs. unshaved axillae (least squares mean, 531 ng/dL vs. 626 ng/dL, respectively; P = 0.011). This difference is not considered clinically significant. The 95% confidence intervals for AUC(0-24) , AUC(0-72) , and Cmax fell within the traditional bioequivalence limits of 0.8 to 1.25. Incidence of treatment-emergent adverse events (TEAEs) was low (<15%) in each treatment arm, and most TEAEs were mild. CONCLUSIONS: Absorption of testosterone 2% solution was unaffected by use of deodorant/antiperspirant or by the presence or absence of axillary hair. Testosterone solution was generally well tolerated.

Skin exposure to deodorants/antiperspirants in aerosol form.

Many cosmetic products are available in spray form. Even though the principal targets of these products are the skin and hair, spraying leads to the partitioning of the product between the target and the surrounding air. In the previous COLIPA study (Hall et al., 2007) the daily use of deodorant/antiperspirant (Deo/AP) in spray form was quantified in terms of the amount of product dispensed from the spray can, without specifically quantifying the product fraction reaching the skin during use. Results of the present study provide this additional information, necessary for a reliable safety assessment of sprayed Deo/AP products. In a novel experimental approach the information obtained from real-life movement analysis (automated motion imaging) of volunteers using their own products was integrated with the aerosol cloud sampling data obtained from the same products, leading to the computation of the product deposited on the skin. The 90th percentile values, expressed as percent deposition relative to the can weight loss after spraying, are 23.5% and 11.4% for ethanol-based and non-ethanol-based products, respectively. Additionally, the study has generated data on the skin area covered by the products, spray duration time, spray angle and spray distance from the skin.

Contact allergens for armpits--allergenic fragrances specified on deodorants.

According to the so-called "26 allergens rule" 26 supposedly allergenic fragrances must be specified on the containers of cosmetic products if they are present above 0.001% in leave-on products and, 0.01% in rinse-off products. This declaration is meant to inform the consumers of potential risks of skin sensitizers in the products. As many consumers of deodorants suffer from allergic or irritant contact dermatitis in the axillae, the presence of allergens in deodorants deserves special attention. The objective of this study was to find answers to the following questions: Does compulsory labeling lead to omission of strong allergenic fragrances in deodorants? Is there a difference in the use patterns of strong and weak allergens? What is the quantitative exposure to fragrances by deodorants? Is the situation in Germany different from other European countries? Is there a difference between deodorants for men and for women? I tested the implementation of the "26 allergens rule" and compiled which allergenic fragrances are specified on the containers of deodorants. Three market studies were conducted in Germany in 2008, 2010 and 2011. The labels of a total number of 374 deodorants were analyzed as to whether any of the "26 allergens" were listed. The frequency of each allergen in the deodorants was compared with results from previous studies by other authors. It was found that up to 83% of the deodorants contain at least one of the "26 allergens" and that up to 30% of all products contain strong allergens above the threshold for labeling (0.001% in the product). The most frequently listed allergens are medium or weak allergens. In comparison with other authors, the frequency of the "26 allergens" in products is slightly smaller in these recent studies for the German market. There is no significant difference between deodorants for men and women, as far as the labeling of the "26 allergens" is concerned. The results show that the mandatory labeling procedure as designed in the "26 allergen rule" is not suitable to guarantee consumer safety for deodorants. As long as consumers are not informed about allergens in products in an easy to understand and transparent way, a compulsory pictogram on the container should inform them about possible risks.

Rapid determination of free fatty acid content in waste deodorizer distillates using single bounce-attenuated total reflectance-FTIR spectroscopy.

A simple, rapid, economical, and environmentally friendly analytical method was developed for the quantitative assessment of free fatty acids (FFAs) present in deodorizer distillates and crude oils by single bounce-attenuated total reflectance-FTIR spectroscopy. Partial least squares was applied for the calibration model based on the peak region of the carbonyl group (C=O) from 1726 to 1664 cm(-1) associated with the FFAs. The proposed method totally avoided the use of organic solvents or costly standards and could be applied easily in the oil processing industry. The accuracy of the method was checked by comparison to a conventional standard American Oil Chemists' Society (AOCS) titrimetric procedure, which provided good correlation (R = 0.99980), with an SD of +/- 0.05%. Therefore, the proposed method could be used as an alternate to the AOCS titrimetric method for the quantitative determination of FFAs especially in deodorizer distillates.

Sources, concentrations, and risks of naphthalene in indoor and outdoor air.

UNLABELLED: Naphthalene is a ubiquitous pollutant, and very high concentrations are sometimes encountered indoors when this chemical is used as a pest repellent or deodorant. This study describes the distribution and sources of vapor-phase naphthalene concentrations in four communities in southeast Michigan, USA. Outdoors, naphthalene was measured in the communities and at a near-road site. Indoors, naphthalene levels were characterized in 288 suburban and urban homes. The median outdoor concentration was 0.15 µg/m(3), and a modest contribution from rush-hour traffic was noted. The median indoor long-term concentration was 0.89 µg/m(3), but concentrations were extremely skewed and 14% of homes exceeded 3 µg/m(3), the chronic reference concentration for non-cancer effects, 8% exceeded 10 µg/m(3), and levels reached 200 µg/m(3). The typical excess individual lifetime cancer risk was about 10(-4) and reached 10(-2) in some homes. Important sources include naphthalene's use as a pest repellent and deodorant, migration from attached garages and, to lesser extents, cigarette smoke and vehicle emissions. Excessive use as a repellent caused the highest concentrations. Naphthalene presents high risks in a subset of homes, and policies and actions to reduce exposures, for example, sales bans or restrictions, improved labeling, and consumer education, should be considered. PRACTICAL IMPLICATIONS: Long-term average concentrations of naphthalene in most homes fell into the 0.2-1.7 µg/m(3) range reported as representative in earlier studies. The highly skewed distribution of concentrations results in a subset of homes with elevated concentrations and health risks that greatly exceed US EPA and World Health Organization (WHO) guidelines. The most important indoor source is the use of naphthalene as a pest repellant or deodorant; secondary sources include presence of an attached garage, cigarette smoking, and outdoor sources. House-to-house variation was large, reflecting differences among the residences and naphthalene use practices. Stronger policies and educational efforts are needed to eliminate or modify indoor usage practices of this chemical.

A comparative human health risk assessment of p-dichlorobenzene-based toilet rimblock products versus fragrance/surfactant-based alternatives.

A comparison of the human health risk to consumers using one of two types of toilet rimblock products, either a p-dichlorobenzene-based rimblock or two newer fragrance/surfactant-based alternatives, was conducted. Rimblock products are designed for global use by consumers worldwide and function by releasing volatile compounds into indoor air with subsequent exposure presumed to be mainly by inhalation of indoor air. Using the THERdbASE exposure model and experimentally determined emission data, indoor air concentrations and daily intake values were determined for both types of rimblock products. Modeled exposure concentrations from a representative p-dichlorobenzene rimblock product are an order of magnitude higher than those from the alternative rimblock products due to its nearly pure composition and high sublimation rate. Lifetime exposure to p-dichlorobenzene or the subset of fragrance components with available RfD values is not expected to lead to non-cancer-based adverse health effects based on the exposure concentrations estimated using the THERdbASE model. A similar comparison of cancer-based effects was not possible as insufficient data were available for the fragrance components.

[Impact of air fresheners and deodorizers on the indoor total volatile organic compounds].

Indoor air quality is a growing health concern because of the increased incidence of the building-related illness, such as sick-building syndrome and multiple chemical sensitivity/idiopathic environmental intolerance. In order to effectively reduce the unnecessary chemical exposure in the indoor environment, it would be important to quantitatively compare the emissions from many types of sources. Besides the chemical emissions from the building materials, daily use of household products may contribute at significant levels to the indoor volatile organic compounds (VOCs). In this study, we investigated the emission rate of VOCs and carbonyl compounds for 30 air fresheners and deodorizers by the standard small chamber test method (JIS A 1901). The total VOC (TVOC) emission rates of these household products ranged from the undetectable level (< 20 microg/unit/h) to 6,900 microg/unit/h. The mean TVOC emission rate of the air fresheners for indoor use (16 products) was 1,400 microg/unit/ h and that of the deodorizers for indoor use (6 products) was 58 microg/unit/h, indicating that the fragrances in the products account for the major part of the TVOC emissions. Based on the emission rates, the impacts on the indoor TVOC were estimated by the simple model with a volume of 17.4 m3 and a ventilation frequency of 0.5 times/h. The mean of the TVOC increment for the indoor air fresheners was 170 microg/m3, accounting for 40% of the current provisional target value, 400 microg/m3. These results suggest that daily use of household products can significantly influence the indoor air quality.

Effect of hair care and hair cosmetics on the concentrations of fatty acid ethyl esters in hair as markers of chronically elevated alcohol consumption.

Fatty acid ethyl esters (FAEE) can be used as alcohol markers in hair. It was investigated in this study whether this diagnostic method is disturbed by hair care and hair cosmetics. Traces of ethyl myristate, ethyl palmitate, ethyl oleate and ethyl stearate were detected in all of 49 frequently applied hair care products by headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS). The highest concentration was 0.003% in a hair wax. From experiments with separated hair samples of alcoholics as well as from the evaluation of the FAEE concentrations and the data about hair care of 75 volunteers (alcoholics, social drinkers and teetotalers) follows that usual shampooing, permanent wave, dyeing, bleaching or shading are of minor importance as compared to the drinking amount and other individual features. However, false positive results were found after daily treatment with a hair lotion containing 62.5% ethanol, with a deodorant and with a hair spray. As an explanation, it is assumed that FAEE are formed in the sebum glands also after regular topical application of products with a higher ethanol content.

Deodorants: a clinical provocation study in fragrance-sensitive individuals.

Deodorants are one of the most marketed types of cosmetics and are frequently reported as a cause of dermatitis, particularly among fragrance-sensitive persons. The aim of this study was to investigate the ability of deodorants, which had previously caused axillary dermatitis in fragrance-mix-sensitive eczema patients, to provoke reactions on repeated open application tests on the upper arm and in the axillae, and to relate the findings to the content of fragrance-mix constituents in those deodorants. 14 eczema patients performed a 7-day use test with 1 or 2 deodorants that had caused a rash within the last 12 months. 2 applications per day were made in the axilla and simultaneously on a 25 cm2 area on the upper arm. A total of 20 deodorants were tested among the 14 patients. Afterwards, the deodorants were subjected to quantitative chemical analysis identifying constituents of the fragrance mix. 12/20 (60%) deodorants elicited eczema on use testing in the axilla. 8/12 deodorants were positive in the axilla on day (D) 7 and 4 both in the axilla and on the upper arm. 2 of the 4 developed a reaction in the axilla before it developed on the upper arm. Chemical analysis revealed that 18/19 deodorants contained between 1 and 6 of the fragrance-mix constituents, on average 3 being found. The mean concentration of fragrance-mix constituents was generally higher in the deodorants causing a positive use test, as compared with those giving a negative reaction, indicating that the differences between the deodorants in terms of elicitation potential were more related to quantitative aspects of allergen content than of a qualitative nature. It is recommended that deodorants are tested in the axilla in the case of a negative use test on the upper arm and a strong clinical suspicion.

Deodorants on the European market: quantitative chemical analysis of 21 fragrances.

Deodorants are one of the most frequently used types of cosmetics and side-effects from them are common. Recent studies relate perfume allergy to this type of product. 73 deodorants were analyzed by gas chromatography--mass spectrometry for the determination of the contents of 7 wellknown fragrance allergens from the fragrance mix and 14 other commonly used fragrance materials. The deodorants were purchased at retail outlets in 5 European countries. It was found that in general, fragrance mix ingredients were more frequently present in vapo- and aerosol sprays than in roll-on products. The levels of the fragrance mix substances ranged from 0.0001-0.2355%. The products investigated contained cinnamic aldehyde and isoeugenol less frequently (17% and 29% respectively), and eugenol and geraniol most frequently (57% and 76% respectively). The 14 other fragrance materials were found in 40-97% of the deodorants, with hedione and benzyl acetate the most frequently found substances. The concentration of these 14 substances ranged from 0.0001-2.7%. It is concluded that the levels of cinnamic aldehyde and isoeugenol found in the deodorants could prove to be relevant for elicitation of contact dermatitis. No conclusions could be drawn about the other fragrance mix constituents, as threshold levels in sensitized individuals have not been investigated. Furthermore, all of the fragrance materials investigated were frequently found in deodorants and, apart from the fragrance mix ingredients, the extent of problems with sensitization to these fragrance materials is largely unknown.

Toxic effects of air freshener emissions.

To evaluate whether emissions of a commercial air freshener produced acute toxic effects in a mammalian species, the authors allowed male Swiss-Webster mice to breathe the emissions of one commercial-brand solid air freshener for 1 h. Sensory irritation and pulmonary irritation were evaluated with the ASTM-E-981 test. A computerized version of this test measured the duration of the break at the end of inspiration and the duration of the pause at the end of expiration--two parameters subject to alteration via respiratory effects of airborne toxins. Measurements of expiratory flow velocity indicated changes in airflow limitation. The authors then subjected mice to a functional observational battery, the purpose of which was to probe for changes in nervous system function. Emissions of this air freshener at several concentrations (including concentrations to which many individuals are actually exposed) caused increases in sensory and pulmonary irritation, decreases in airflow velocity, and abnormalities of behavior measured by the functional observational battery score. The test atmosphere was subjected to gas chromatography/mass spectroscopy, and the authors noted the presence of chemicals with known irritant and neurotoxic properties. The Material Safety Data Sheet for the air freshener indicated that there was a potential for toxic effects in humans. The air freshener used in the study did not diminish the effect of other pollutants tested in combination. The results demonstrated that the air freshener may have actually exacerbated indoor air pollution via addition of toxic chemicals to the atmosphere.