Saturday, February 13, 2016

Glass manufacturing update for chromium


Since I put up my recent post on cadmium (Cd) and arsenic (As), attention in SE Portland (OR) has shifted to the possibility of hexavalent chromium pollution in the area around Bullseye glass. To try to help everyone understand the data for Cr(VI), I'm adding this post, but a word of caution at the outset: the data for chromium are far less clear.

First off, everyone needs to understand that there are two common forms of chromium used in industry. Cr(III), or trivalent chromium, does not have documented health risks; it is the form of chromium found most often in the human body. Cr(VI), or hexavalent chromium, is more dangerous, because it is a powerful oxidant; it strips 3 electrons off other atoms or ions in converting to Cr(III). If you've heard of oxidative damage, this is an example. You could write these as Cr3+ and Cr6+, but I can't get Blogger to do superscripts...so they look funny.

Hexavalent chromium, therefore, is the form of the element that matters for health risk, and all the standards I can find are for Cr(VI), including the ones in the following table, which again combines DEQ air monitoring data with Oregon benchmarks, EPA cancer risks, and reference values for non-cancer health effects. I left the Cd and As rows in for comparison. Everything here applies to inhalation risk, with units of micrograms/cubic meter.


You may notice that the DEQ measurements are noticeably higher for chromium, while EPA cancer risk threshold is lower. There is, however, a huge uncertainty here: we don't know how much of the chromium DEQ measured is Cr(VI) - hexavalent chromium. In the data sheet, there is no benchmark reported for "unspeciated" chromium, which means a mix of chromium in different oxidation states like Cr(III) or Cr(VI). It seems very likely that the method used to monitor chromium was something like mass spectrometry, which identifies Cr by its atomic weight but does not distinguish the oxidation state. So all we can be sure of from the data is that the amount of Cr(VI) is less than or equal to 0.0715 micrograms/cubic meter on average at the monitoring station.

The other uncertainty is whether the bulk of the chromium is coming from Bullseye at all. While the monitoring station is close by, we haven't got a relative concentration map for chromium from the moss and lichen sampling done by the US Forest Service, as we do for cadmium and arsenic. In the case of those metals, the USFS study pointed pretty clearly to Bullseye's location. It does seem that Bullseye was using Cr(III) and Cr(VI), since they have suspended production with Cr(VI) but not Cr(III) at DEQ's request. However, the company claims that its factory was not operating on the peak days of chromium emission; there are indeed two days with much higher (roughly 20X) chromium emissions in the DEQ data that are responsible for most of the average (66% of the total emissions measured come from those two days). While a correspondence between cadmium and arsenic points to glassmaking as an industry, and Cr(VI) salts like potassium chromate and dicrhomate are used to color glass, lots of industries use Cr(VI) salts, for example for the chrome plating industry. We also don't have the benefit of knowing (from the moss and lichen monitoring) how quickly the chromium exposure lessens - if at all - as one moves away from the DEQ monitoring station. In sum, the source of the chromium in the DEQ data is unclear at this point.

Given those caveats, the chromium levels are still concerning. If the source of the chromium is industrial, it is quite possible that it is indeed mostly Cr(VI). In that case, the lung cancer risk from chromium exposure at the monitoring station is close to 1 in 1,000 for someone breathing that air 24/7 for a lifetime using the EPA model. That is still much lower than the baseline lung cancer risk, but if you eliminate the effect of smoking (which is linked to about 90% of lung cancer), this potential Cr(VI) risk might add as much as 14.5% to the risk of lung cancer from all causes except smoking - a worst-case scenario for someone living at the monitoring station. That's still only about a sixth of the contribution of radon exposure (you have had your house radon-checked, right?), but it's potentially more than for cadmium or arsenic. The non-cancer risks don't look too bad; they are actually far below the level where particulate emissions cause non-cancer disease, and the EPA has low confidence in the study that gives the much lower threshold for mist and aerosol exposure, for what look to my eyes like great reasons (see the "Chronic effects - noncancer" section in the IRIS summary).

So the picture for chromium is much more vague. It would be great, for example, to know how much of the chromium DEQ is finding in the air is hexavalent. It is possible to distinguish the hexavalent chromium ion, but to do a Cr(VI)-specific test requires an extra separation step (silica gel chromatography) that was presumably not part of the DEQ protocol. It would also be very helpful to know if the USFS data includes relative chromium levels, even if those samples don't distinguish the oxidation state, to help pinpoint the source of the emissions. Those avenues should definitely be pursued; the existing DEQ emissions data give us a worst-case risk that is not minor. Further data would let us know just how close we actually are to that worst case.

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