Real-time emissions of volatile organic compounds in the cabin
Unlike tailpipe emissions, Vehicle Interior Air Quality (VIAQ) is lightly regulated. In the broad area there are existing ISO and SAE standards, and an active United Nations Economic Commission for Europe (UNECE) working group. Some countries have national standards, in particular Japan, Korea, China and Russia. There are 97 VOCs listed as hazardous air pollutants in Title III of the Clean Air Act Amendments of 1990. Overall, the arc of regulation is at an early stage, covers a limited number of pollutants, and has much lower priority and profile compared to the exhaust pipe post-Dieselgate. Nevertheless, the total health exposure of drivers is significant and under-measured.
VIAQ breaks down into three broad areas. The first concerns ingress of pollution into the cabin, especially particles. The second looks at the build-up of pollutants from human occupants, including carbon dioxide from respiration. The CEN standardisation workshop #103 in Europe1, initiated by the AIR Alliance and building on initial test work by Emissions Analytics, is considering these first two elements. The third area, and the subject of this newsletter is the car interior itself and its capacity to emit volatile organic compounds (VOCs) over the life of the vehicle.
What might be colloquially and informally referred to as ‘new car smell’ has typically been ignored, partly because it has been difficult to measure. Recent advances in instrumentation now allow the measurement of not only total, time-weighted average VOCs, but it can now distinguish between different species of VOCs in real time.
Emissions Analytics and Cambridge, UK-based Anatune have worked together to test this ‘new car smell’. The subject has a particular resonance in Asia. 11.2 per cent of buyers in China complained about the odours they found in their new cars, according to the 2019 JD Power China Initial Quality Study.
Car interiors, comprising dozens of separate materials ranging from natural textiles to synthetic polymers and adhesives, emit a wide range of VOCs, among them acetaldehyde. Symptoms that customers have cited range from sore eyes to nausea and headaches, and aggravated respiratory conditions.
Acetaldehyde is especially problematic, owing to the fact that many Asians possess a less functional acetaldehyde dehydrogenase enzyme, responsible for breaking it down. This regional genetic characteristic is one reason why the strictest regulation of VOCs exists in the key Asian markets China, Japan and Korea, and why manufacturers typically observe these regulations for cars that will be sold globally.
However, acetaldehyde is merely one of dozens of VOCs that a car produces. The sources are typically: •Residual compounds from the manufacturing process and material treatment of different interior components and textiles
•Adhesives and carrier solvents that will de-gas – as much as 2kg of adhesive can be found in a modern car, much higher than in the past where mechanical riveting and bolting was more common
•Degradation of cabin materials over the longer term as a result of oxidation, ultra-violet light and heat.
The following table sets out the regulated limits in key Asian countries, in micrograms per metre cubed, and the potential human symptoms from exposure.
In this testing, not only did we manage to isolate different VOCs, but we quantified their mass using SIFT-MS, a type of direct mass spectrometry that uses precisely controlled soft ionisation to enable real-time, quantitative analysis of VOCs in air, typically at detection limits of parts-per-trillion level by volume (pptv).
Anatune provides chromatography and mass spectrometry-related analytical solutions, in particular the deployment of SIFT-MS, which stands for Selected Ion Flow Tube Mass Spectrometry and is built by the Christ Church, New Zealand-based company Syft Technologies. One of the main advantages over existing instrumentation is that SIFT-MS measures multiple analytes in real time, akin to a rolling video compared to the ‘snap shot’ of traditional chromatography.
As with any technology, there is a trade-off with the more traditional technique of thermal desorption/gas chromatography (TD/GC) analysis, where VOCs are collected on sorbent tubes on an integrated basis. The SIFT-MS approach cannot distinguish every analyte, and the most effective way to operate the instrument requires ‘telling it’ what you are looking for in advance.
In an initial test of a one-year-old gasoline Hyundai i10, Anatune deployed the Syft Technologies’ Voice 200ultra.
The car was tested every 15 minutes for 60 seconds over five hours on an early summer’s day, where temperatures rose to 20 degrees Celsius (68 degrees Fahrenheit). The measured concentrations were expressed as the mean across the 60-second duration of the sample. For the final 15-minute vent cycle, the car windows were opened, the car started and the air conditioning run at full power. The SIFT-MS then sampled continuously using the above conditions for the full 15 minutes.
The two principle outcomes of the test concern the steady accumulations of ten VOCs as temperatures rose; and the unexpected dynamic of emissions during the final fifteen minutes.
Most noticeably, the common solvents methanol and acetone rose from very low base points (18 and 12 micrograms per cubic metre) to 935 and 576 μg/m3 respectively. The 52-fold rise in methanol is noteworthy. While it is a very common solvent and not directly regulated, it is toxic and could be an irritant at these levels.
The only exception to these across-the-board rises was benzene, which fell from 17 to 15 μg/m3. However, this is where the final fifteen minutes revealed unexpected results.
Despite windows being open and the air conditioning turned on, some VOCs such as acetaldehyde rose steeply during the fourth to sixth minutes. During this phase acetaldehyde concentrations rose from an initial base of approximately 50 to 550 μg/m3, more than ten times the regulated limit in China and Japan.
Anatune Senior Application Chemist and SIFT-MS Specialist Dr Mark Perkins hypothesises that the car’s Heating and Ventilation system (HVAC) may form a type of ‘sink’ for some VOCs. When the venting or AC are activated, the sink is flushed out into the cabin causing a pronounced spike. Three other analytes that rose in the same time frame included styrene, toluene and benzene.
From a vehicle testing perspective, the ability to detect and speciate different analytes in real time opens up the possibility for more extensive research of exposure and the potential for regulation to reduce detrimental health exposures. It could also assist driver education in respect of ‘VOC build-up’ when a vehicle is parked in hot weather.
Overall what this shows is that a four-hour, time-weighted average of total VOCs – the basis of existing regulatory testing – could be improved. Future regulations will need to cover individual materials in isolation as well as ‘whole car testing’, by which we mean the actual, real-world way in which the many materials comprising a car interior act dynamically with each other and within the HVAC system.
With so many new entrants into the global car manufacturing sector, and at a time of drivetrain and material changes often connected with light-weighting, there has never been a more critical juncture at which to take seriously chemical emissions that can harm vehicle occupants and are already the source of a high volume of complaints.
Regulations should reflect where there is market failure, in particular where a consumer does not realise or cannot do anything about the health exposure. ‘New car smell’ may be unpleasant to certain consumers, but there is little understanding of the health detriment. Acetaldehyde is one of the better understood VOCs in the cabin so far, which was prominent on the vehicle tested, and which should be considered for early intervention.
1 CEN Workshop 103 held its first meeting on 4 November 2019, chaired by not-for-profit organisation the AIR Alliance, whose co-founder is Emissions Analytics’ founder and CEO Nick Molden