Protein fraud - urgent topic for Chromforum discussion

[Einar Ponten]

Dear All,
Considering the disaster in China I think it would be valuable if this community react and discuss the topic more in detail.

By adding nitrogen containing compounds, like melamine, cyanuric acid, etc to mislead Kjeldahl analysis for proteins, criminals actually are poisoning infants in the age of 1-3 years, i.e., 4% of the population in China roundabout 40-50 million children.

Obviously also the indirect effects are significant. EU warns for bisquits and chocolate from China and today FDA warned people for instant coffee product since these contain milk powder that is an enriched source of the triazines http://www.fda.gov/bbs/topics/NEWS/2008/NEW01891.html


There is an urgent need to secure people health and product quality.

Please let us discuss what approach you are using to meet this analytical problem for different matrices, it is our responsibility.

[Bruce Hamilton]

Actually, if this is to be discussed, then it may be better in the general around the water cooler forum, as a range of techniques can be used to measure melamine and other fraudulent food additives.

In general, the issue of measuring these additives, and the development of methods will be the responsibility of either regulators or companies involved in these markets.

According to a news item, there are plans for experts from several of the affected countries to meet over the next week or two to discuss the harmonisation and appropriateness of analytical techniques for melamine and other adulterants.

It already appears that one government minister has just resigned ( in Taiwan ) because of the issues of their regulators LOD or LLOQ. It appears their govt said no melamine was acceptable, but there analytical method LLOQ ( or LOD - the news item wasn't clear ) was only 2.5 ppm, so they then publicly said that 2.5 ppm or above would be banned.

That caused outrage, so the minister resigned, and they are looking at "None" again, which is just another way of using the same data.

However, they are likely to look at their methods, given that some other countries can report down to 1 ppm or lower ( NZ has set 1 ppm for infant products and 5 for others , and the 1 ppm is apparently the LLOQ ).

The European Food Safety Authority has just updated their Melamine TDI review ( Tolerable Daily Intake ), and are still sticking to 0.5 mg/kg, which is used to arrive at the above detection limits. The detection limits will help determine the analytical procedures.

Other key factors that affect the analytical protocols may be the need to measure the presence of cyanuric acid and possibly other adulterants ( such as urine and skin products ) that have also been used to elevate Kjeldahl measured nitrogen contents of food products. There have
been suggestions that some processing was used to make the melamine less chemically obvious, but I've seen no reported evidence in news items.

It's not clear to me that cyanuric acid is added as adulterant, I suspect it's formed from the melamine during processing or metabolism.

There is a lot of knowledge from the USA's pet food tragedy, and I expect much of that has already been freely transferred to regulators elsewhere.

I can't see how discussions here will progress the situation, but perhaps it may help people understand some of the analytical issues. Whilst I've provided some references to people who wanted them, I would expect laboratories to link to a established correlation programme before producing data, as sample preparation and standards will be very important.

Please keep having fun,

Bruce Hamilton

[tom jupille]

Per Bruce's suggestion, I've moved the discussion; it really does go beyond simply liquid chromatography.

[Schmitty]

We use the FDA method for requsts of this analysis. Since the matrices are varied, we perform spike recovery with each different matrix.

http://www.fda.gov/cvm/GCMSMelamine.htm

We are looking into an LCMSMS method in order to establish a lower LOD/LLOQ. The chromatography with an Agilent 5973 using the FDA method is sufficient at 10ppm, however it is very unlikely to be acceptable at 1ppm, with my current testing. The 5975 is better at 1ppm, sensitivity-wise, however the lack of significant sample cleanup is leading us in the direction that GCMS is not going to work with the current method at 1ppm...therefore the LCMSMS avenue.

[Peter Apps]

The aldulteration of food with melamine and other nitrogen boosters would disappear quickly if techniques like Kjeldahl that measure nitrogen content were to be abandoned in favour of measurements of protein per se.

Peter

[JGK]

I understand from the news reports following the resignation of the chinese minister responsible for food standards that many of the companies involved were actually "exempt" from the testing programmes as it was felt that they should "Self Regulate".

However, it would seem that in the pursuit of profit standards fall.

This is possible the greatest advert for independent food testing ever made. It's a pity that so many lives may be lost/ruined inthe process.

[Bruce Hamilton]

Whilst some companies were "exempt", it was after they had convinced the food safety authority that they tested the products according to agreed standards. I think they had to show testing was acceptable for three batches. However, the industry only routinely checks for biological markers of product quality, such as bug counts, not illegal adulteration..

The issue is that the testing is based on typical measurements of the quality of dairy milk, not illegal adulturation of the milk. The Kjeldahl method is a fast and effective indicator of protein but, like other tests, it's compromised by deliberate criminal activities.

The suggestion that protein testing would have detected the melamine is true, however it would not have detected other forms of adulteration involving cheap protein sources from animal processing waste products that have also been found in dairy products in the past, along with the easily-detected urine and urea wastes..

The solution is to make the supply chain honest, not try to outsmart criminals by testing. That's what quality systems try to achieve, and assurance testing should be part of that process.

One of the issues in this tragic case is that regional authorities had major incentives to meet economic growth targets, and hence hide any inconvenient facts that might compromise that regional growth.

Also loyal party members were given major positions in industry, whilst still retaining positions in the govt - which enabled them to prevent the release of embarrassing information.

Despite recent news items coming out of China suggesting that Chinese govt agencies uncovered the criminal fraud, it's clear that it was New Zealand Prime Minister's direct message to the Chinese central government in early September that triggered the Chinese govt's response, as the Chinese govt food quality agencies had known about the adulteration since early August.

That's the same time at the NZ shareholder ( Fonterra ) was first informed, and they immediated pushed for a public recall, but were overridden by the majority shareholders and local authorities, and the Chinese govt quality agency still did nothing - hence the departure of the agency head once publicity appeared.

The NZ shareholder eventually decided they escalate it to high political levels, and asked the NZ govt to convey their concerns. The tragedy shows why quality systems have to be clearly separated from business and political interests, and must be systemic from grower to consumer.

As the adulteration issue disappears, it's likely that melamine found will come from residual insecticide degradation, such as from cyromazine, and may highlight yet another common aspect of inadequate control of food quality.

Once again, the acceptable and responsible usage of such chemicals should rest with the initial user, with quality checks to ensure all is well, rather than trying to outsmart criminals.

Bruce Hamilton

[efoconnor]

Nations should not accept any testing for food products that will not specifically identify melamine. The Kjeldahl method is useless. The chinese are exploiting a stupidity we must eliminate. Chinese products must not be allowed in unless they pass a melamine test.

[WK]

Out with classic analytical chemistry and in with as much chromatography as possible - preferably with MS on the end. Especially when its public health involved. LC-MS should have more widespread use.
I can remember the European wine scare of the 80s - that created a lot of work.
There should also be less bean-counters in charge of us!
Less talk of cost - more talk of the value...
WK

[rhaefe]

WK,

You do remember the "Austrian wine scandal" from 1985, eh?
Our University lab received quite a few bottles of wine to be analyzed by LC. Most of them turned out to be OK (=diethylene glycol free, not necessarily OK quality wise).
Most people didn't want their wines returned back to them so the bottles had to be disposed of by us undergrad and grad students...

Robert

Austrian ExPat

[Jade.Barker]

Most people didn't want their wines returned back to them so the bottles had to be disposed of by us undergrad and grad students...

Wow, way to sacrafice for science, we should all follow this brave example.