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Gloves, Québec’s (Canada) Institut de recherche Robert-Sauvé en santé et en sécurité du travail, and a workplace nanotoxicity methodology report

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A new report on a workplace health and safety issue in regard to nanoparticles (Development of a Method of Measuring Nanoparticle Penetration through Protective Glove Materials under Conditions Simulating Workplace Use)  was released in June 2013 by Québec’s Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST). Little research has been done on exposure through skin (cutaneous exposure), most research has focused on exposure by inhalation according to the report (en français version here),

In the workplace, the main pathway to NP exposure is inhalation (Ostiguy et al., 2008a). Exposure by the cutaneous route has not been studied much, partly because of the widely held belief that skin offers an impermeable barrier to NPs (Truchon et al., 2008). Yet a growing number of studies have pointed to the possible percutaneous absorption of NPs, such as in the case of skin damaged by abrasion (Zhang et al., 2008), repeated flexion (Rouse et al., 2007) or even through intact skin (Ryman-Rasmussen et al., 2006). Pores, hair follicles and sweat glands may also play a role in facilitating absorption of NPs through the skin (Hervé-Bazin, 2007). The nanoparticles are then carried throughout the body by the lymphatic circulatory system (Papp et al., 2008). Induced direct toxic effects have also been reported for epidermal keratinocyte cells exposed to carbon nanotubes and other types of NPs (Shvedova, 2003). [p. 17 PDF version; p. 1 print version; Note: See report bibliography for citations]

The researchers examined gloves made of four different types of material: nitrile, latex, neoprene, and butyl rubber under a number of different conditions. One type of nanoparticle was used for the study, titanium dioxide in powder and liquid forms. The report summary provides a bit more detail about the decision to develop a methodology and the testing methods,

With the exponential growth in industrial applications of nanotechnologies and the increased risk of occupational exposure to nanomaterials, the precautionary principle has been recommended. To apply this principle, and even though personal protective equipment against nanoparticles must be considered only as a last resort in the risk control strategy, this equipment must be available. To respond to the current lack of tools and knowledge in this area, a method was developed for measuring the penetration of nanoparticles through protective glove materials under conditions simulating workplace use.

This method consists of an experimental device for exposing glove samples to nanoparticles in powder form or in colloidal solution, while at the same time subjecting them to static or dynamic mechanical stresses and conditions simulating the microclimate in the gloves. This device is connected to a data control and acquisition system. To complete the method, a sampling protocol was developed and a series of nanoparticle detection techniques was selected.

Preliminary tests were performed using this method to measure the resistance of four models of protective gloves of different thicknesses made of nitrile, latex, neoprene and butyl to the passage of commercial TiO2 nanoparticles in powder form or colloidal solution. The results seem to indicate possible penetration of the nanoparticles in some types of gloves, particularly when subjected to repeated mechanical deformation and when the nanoparticles are in the form of colloidal solutions. Additional work is necessary to confirm these results, and consideration should be given to the selection of the configurations and values of the parameters that best simulate the different possible workplace situations. Nevertheless, a recommendation can already be issued regarding the need for regular replacement of gloves that have been worn, particularly with the thinnest gloves and when there has been exposure to nanoparticles in colloidal solution.

For interested parties, here’s a citation for and a link to the report (PDF),

Development of a Method of Measuring Nanoparticle Penetration through Protective Glove Materials under Conditions Simulating Workplace Use by Dolez, Patricia; Vinches, Ludwig; Perron, Gérald; Vu-Khanh, Toan; Plamondon, Philippe; L’Espérance, Gilles; Wilkinson, Kevin; Cloutier, Yves; Dion, Chantal; Truchon, Ginette
Studies and Research Projects / Report  R-785, Montréal, IRSST, 2013, 124 pages.

I last wrote about gloves and toxicity in a June 11, 2013 posting about gloves with sensors (they turned blue when exposed to toxic levels of chemicals). It would be interesting if they could find a way to create gloves with sensors that warn you when you are reaching dangerous levels of exposure through your gloves. Of course, first they’d have to determine what constitute a dangerous level of exposure. The US National Institute of Occupational Health and Safety (NIOSH) recently released its recommendations for exposure to carbon nanofibers and carbon nanotubes (my April 26, 2013 posting). In layperson’s terms, the recommended exposure is close to zero exposure. Presumably, the decision was based on the principle of being ‘safe rather than sorry’.

One final comment about exposure to engineered nanoparticles through skin, to date there has been no proof that there has been any significant exposure via skin. In fact, the first significant breach of the skin barrier was achieved for medical research, Chad Mirkin and his team at Northwestern University trumpeted their research breakthrough (pun intended) last year, from my July 4, 2012 posting,

Researchers at Northwestern University (Illinois, US) have found a way to deliver gene regulation technology using skin moisturizers. From the July 3, 2012 news item on Science Blog,

A team led by a physician-scientist and a chemist — from the fields of dermatology and nanotechnology — is the first to demonstrate the use of commercial moisturizers to deliver gene regulation technology that has great potential for life-saving therapies for skin cancers.

The topical delivery of gene regulation technology to cells deep in the skin is extremely difficult because of the formidable defenses skin provides for the body. The Northwestern approach takes advantage of drugs consisting of novel spherical arrangements of nucleic acids. These structures, each about 1,000 times smaller than the diameter of a human hair, have the unique ability to recruit and bind to natural proteins that allow them to traverse the skin and enter cells.

This goes a long way to explaining why primary occupational health and safety research has focused on exposure via inhalation rather than skin.  That said, I think ensuring safety means minimizing exposure by all routes until more is known about the hazards.

Glove sensors and toxic substances

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Gloves that change colour as a signal you’re handling toxic substances have been developed by a research team at  the Fraunhofer Institute according to a May 2, 2013 Fraunhofer Research Institution for Modular Solid State Technologies EMFT news release (also on EurekAlert as a re-issued June 7, 2013 news release),

Employees in chemical production, the semiconductor industry or in laboratories are frequently exposed to harmful substances. The problem: Many of these aggressive substances are imperceptible to human senses, which makes handling them so risky. That’s why there is a broad range of solutions that employers can use to protect their staff from hazardous substances – from highly sensitive measuring equipment to heat imaging cameras. Soon, this spectrum will be enhanced by one more clever solution that is easy to handle, and that dispenses with a power supply. Researchers at the Fraunhofer Research Institution for Modular Solid State Technologies EMFT in Regensburg have engineered a glove that recognizes if toxic substances are present in the surrounding air.

Here’s an image of the glove,

The sensor glove turns blue in the presence of hazardous substances. (© Fraunhofer EMFT)

The sensor glove turns blue in the presence of hazardous substances. (© Fraunhofer EMFT)

The news release provides more details,

The protective glove is equipped with custom-made sensor materials and indicates the presence of toxic substances by changing colors. In this regard, the scientists adapted the materials to the corresponding analytes, and thus, the application. The color change – from colorless (no toxic substance) to blue (toxic substance detected), for example – warns the employee immediately. …

….

The warning signal is triggered by an indicator dye integrated into the glove that reacts to the presence of analytes, in this case, the toxic substances. The experts at EMFT used a variety of techniques in order to furnish textiles with sensor-activated dyes. The sensor-activated dyes are applied to the clothing with the customary dye and print process, for example, by affixing them in an immersion bath. Previously, the researchers used targeted chemical modification to adapt the color molecules to the fiber properties of the respective textile. Alternatively, the textiles can also be coated with sensor particles that are furnished with sensor dyes. For this purpose, the scientists integrated the dye molecules either into commercial pigments or they built them up on an entirely synthetic basis. The pigments are then manufactured according to the customary textile finishing process, for instance, the sensor particles are also suitable for silkscreening. “Which version we opt for depends on the requirements of the planned application,” says Trupp [Dr. Sabine Trupp, head of the Fraunhofer EMFT Sensor Materials group].

The challenge lies foremost in the tailored development of sensor dyes. “The dye molecule must detect a specific analyte in a targeted manner – only then will a chemical reaction occur. Moreover, the dye must adhere securely; it cannot disappear due to washing. We aim for the customer’s preferences in the color selection as well. All of these aspects must be kept in mind when developing the molecule and pigment properties,” explains Trupp.

The technology could be extended to do more and could be adapted for other applications (from the news release),

The expert already has new ideas about how the solution could be developed further. For example, a miniaturized sensor module, integrated into textiles, could record toxic substances, store the measurement data and even transmit them to a main unit. This way, you could document how frequently an individual within a hazardous environment was exposed to poisonous concentrations over a longer period of time.

The researchers also envision other potential applications in the foodstuffs industry: In the future, color indicator systems integrated into foils or bottle closures are intended to make the quality status of the packaged foods visible. Because the sell-by date does not represent a guarantee of any kind. Foodstuffs may often spoil prematurely – unnoticed by the consumer – due to a packaging error, or in the warehousing, or due to disruptions in the refrigeration chain. Oil-based and fat-containing products are specifically prone to this, as are meats, fish and ready meals.

The notion that food packaging could be designed to include sensors that alert consumers and retailers about product spoilage is not new and was mentioned recently and briefly in my Mar. 25, 2013 posting which featured excerpts from an interview with biotechnologist Christoph Meili about nanotechnology-enabled food packaging.