More challenges in the Greenpeace detox campaign
More challenges in the Greenpeace detox campaign
Just days after our recent report, Greenpeace released a new interesting study “Toxic Threads: The Big fashion stitch-up”[i], to build on their detox campaign. The study provided data for cancer-causing amines, NPE´s and toxic phthalates in garments collected all over the world. More global brands were included in the study compared to earlier reports. With this new initiative the pressure on the big fashion brands will further increase.
Technical challenges of particular concern
Let us put some technical issues in the spotlight of which we think are especially important in the context.
Some of them are already included in the detox story, some not.
Many of the underlying ecological issues related to textiles are still not well known to decision makers and to eco compliance officers in retailers and textile processing companies, due to lack of knowledge of product compositions and chemical processes, as well as lack of knowledge of possible risks associated with it. In many cases not the dyes and chemicals which are used are the real problem, often the real problem are byproducts from the manufacturing of these dyes and chemicals. Important products used in the textile industry, even involving the most common reactive and disperse dyes used in the world, may contain critical contamination by toxic substances.
Just to mention a few examples, more specifically, many high volume textile dyes may contain critical contaminants
- banned amines in reactive dyes
- chlorinated aromatic compounds in vat and disperse dyes
- aniline in blue jeans
Banned amines in reactive dyes
Greenpeace made clear that according to their point of view even low amounts of 7-9 ppm of banned amines would be objectablei, although far below the strictest regulatory limits. But it seems so far Greenpeace has only looked at some niches related to the use of prohibited direct dyes linked with certain amines such as o-dianisidine. But potentially there are further significant concerns : the content of p-chloroaniline (PCA) linked with reactive dyes.
The most significant case known in the industry is the banned amine p-chloroaniline (PCA)[ii] in reactive dyes, such as C.I. Reactive Black 5 which is the most important reactive dyes of all, volume-wise more than 100.000 metric tons , contributing to half of the total world demand of reactive dyes. The occurrence of PCA in reactive dyes is well known since the middle of the 1990s, and linked with specific intermediates such as Parabase[iii] . In the manufacturing of parabase, p-chloroaniline was found as a by-product in amounts of 500-2000 ppm, according to a DyStar paperiii. Subsequent process optimizations have reduced the amount of PCA and mitigated the problem, today suppliers typically specify “< 500 ppm of PCA” in Parabase[iv]. During synthesis of the dyes, the PCA is chemically converted and ends up in the final product[v]. However, upon subsequent reductive cleavage in the environment or in biological systems it may be released again. The PCA specification on the intermediate stage must be controlled to meet the legally allowed 30 ppm[vi], respectively 20 ppm of eco labels such as Oeko-Tex 100[vii], regarding the levels of cleavable prohibited amines on the fabrics. Certain manufacturers have even stricter specifications, to be on the safe side. One has to understand that underlying products such as Reactive Black 5 and black mixtures based upon Reactive Black 5 are rock bottom commodity products. Not every player in a fierce market environment sticks to this requirement, especially when operating in markets that do not have legal thresholds as in the EU. And even if the mentioned requirements of 20-30 ppm PCA content are safely met, it is obvious that some amount of PCA containing products are released to the effluent during textile processing, since the fixation yield in dyeing is far less than 100%. And further a legally allowed threshold does not necessarily mean it would be best available technology or inevitable contamination, and the legally allowed level of 30 ppm would be the ultimately desirable threshold value.
Chlorinated aromatic compounds (PCP, PCB, dioxins)
In disperse dyes polychlorinated aromatic compounds (polychlorinated biphenyls- PCBs[viii], polychlorinated phenols-PCPs [ix], toluenes & benzenes, dioxins, …) may be contained as by-products. A known critical example is Disperse Orange 30, of which only very few players in the world can supply a clean product.
Even the contamination with the notorious seveso-dioxine[x], one of the most toxic chemicals known, has been reported as contaminant in textiles and linked with textile allergies[xi], [xii]. Service providers offer specialized testing services to measure the level of dioxine in textiles[xiii] . The occurrence of dioxine was brought in context with the use of certain dyestuffs and with the use of pesticides. More specifically, dioxines have been linked with certain vat and direct dyestuffs derived from the organic intermediate chloranil[xiv], a dyestuff intermediate, and the manufacturing of chlorinated phenolsxiv.
These chlorinated phenols are also specified in labels such as Oeko-Tex 100, e.g. Tetrachlorophenol (TeCP) 0.5 ppm and Pentachlorophenl (PCP) 0.5 ppm on the fabric. Translated to the dyes stage 10 pm would be approximately a maximum tolerable limit for TeCP and PCP. Serious and responsible players can safely meet these requirements through process control, tight specifications and by checking of every manufactured lot . However, we have just last year collected in the market black disperse dyes of a market leading Chinese supplier which had contaminates of 128 ppm of PCP and 218 ppm of TeCP[xv], far exeeding these limits, yet during further discussions it became clear that textile processing houses were pretty much unaware of the issues and choose their dyes only based on cheapest available prices.
Aniline in blue jeans ?
Jeans are high fashion since many years, and experienced a remarkable growth over the last decade. Yet only a few insiders are aware of potential health issues.
The by far most important colorant in blue jeans is indigo (C.I. vat blue 1), a blue dyestuff for colouration of cotton. Originally indigo is a natural product from the plant Indigofera tinctoria. Due to more economical mass scale chemical manufacturing indigo had been a major cornerstone in the emergence of the chemical industry in Germany in the last 150 years. Indigo is today made chemically based on aniline[xvi] by the so called Heumann-Pfleger synthesis[xvii], or related methods. Anilin is, according to EPAxvi “a probable human carcinogen“, but yet “there was insufficient evidence to suggest that aniline itself is a cause of bladder tumors”xvi
Alternatively there is also the possibility of a biochemical process to manufacture indigo[xviii], however commercially not competitive against chemical manufacturing – unless there would be a stricter request for product purity and highest ecological standards.
Decades ago indigo was the heart of the German dyestuff manufacturing industry, but today more than 90% of indigo synthesis is made in China, by chemical processes based on aniline. Not surprisingly, trace amounts of aniline may be contained in chemically manufactured indigo, depending on process controls, yields of conversion and optionally further purification steps. According to BASF, indigo does contain up to 0.6% of aniline and 0.4% of n-methylaniline, “despite of a highly developed manufacturing process”, means combined approximately 1% of such undesirable compounds. BASF patented a process for purification of indigo[xix] already in 1991. However, the occurrence of toxic aniline and N-methylaniline in synthetic indigo is still an issue of particular concern, considering the fact that today Chinese players are dominating the world market in the manufacturing of indigo. To what extent they are supplying indigo of pure enough quality is an open question. To what extent aniline and its degradation products would be found on the fabric after dyeing, or released in the effluent, is another important question.
Yet the issue of aniline contamination has only been addressed rarely[xx]. It would be worthwhile to do a systematic study on this particular subject to what extent aniline can be found in jeans by the leading brands blue jeans collections.
How critical is it ? What can be done ?
Alternatives to the above mentioned products with potentially critical contaminants are in many cases available but often avoided due to cost reasons. The contamination is due to the common synthetic manufacturing routes which are used in the chemical industry. Responsible manufacturers know about these issues and know ways to reduce or avoid any contamination below generally accepted tolerance levels, by means of tight process control or by purification steps. However, not all dye manufacturers are well informed and the temptation is high for manufacturers to use cheaper processes, in a market that has as much overcapacity as the total world market demand.
The transition of mass dye production to Asia and the closedown of the European dyes production of the big multinationals as a result of cost pressure, has not made it easier to manage these concerns. Surely there are emerging responsible high quality manufacturers in Asia who can manage according to accepted tolerance limits. It usually implies a price premium, and due to the enormous cost pressure in the industry not everybody is choosing compliant product qualities, and not every textile plant and purchasing manager of the retailers are aware about the risks involved.
Too many people in the industry who know about the issues have adopted a “don´t ask, don´t tell” attitude, unless textiles are really tested and challenged for the specific criteria, nobody really cares.
So far in many cases the critical ingredients were simply discharged with the effluent. Only when critical ingredients were found on the textile in high levels people got concerned. While going from the textile perspective to a more comprehensive perspective including the water quality and EHS standards at the processing house , the picture really changes. This is a potential game changer now when people will have to check and control the effluent loads as well.
For some of the above mentioned contaminants such as prohibited amines there are legal limits and even stricter limitations in ECO label standards such as the Oeko-Tex 100 standardvii. Regarding the legal limits, these are often based on what was state of the art in analytical measurement at the point of time when the regulatory limit was implemented rather than real toxicological or environmental assessments. This means even the today´s accepted levels of critical ingredients may be challenged, since in many cases the threshold levels are historical and based on analytical measurement accuracies which have improved since the implementation of the limits. Furthermore, many products used since long time in the textile industry have never been fully evaluated and only now under the REACh legislation in the EU they will be subject to a full eco-toxicological examination. Some unpleasant surprises may be hidden in the pipeline .
There are other product alternatives available but at a higher cost. Still today, 80% of buying decisions in textile mills are based on price, not on eco compliance, providing a fit-for-purpose quality is achieved. The market is a ruthless buyers market. Textile mills are forced to operate with lowest cost, because of pressure from buyers who want to source cheapest textiles. It should be stressed that the retailers acting accordingly in the most aggressive way are usually not the ones who have already committed to the Greenpeace detox campaign of zero discharge of hazardous substances, although many of them have their own restricted substance lists as a marketing tool as well. Furthermore, it is a fact that the non eco compliant market including major domestic markets represent clearly the biggest part of the market, which is critical enough.
15-20 years ago, people in the European textile industry have discussed full recycling of water, high dye fixation and zero discharge. However, the European textile industry has only contracted since then, and the textile industry has largely migrated to Asia, due to enormous cost pressure imposed by the buyers (retailers) and due to cheaper competitors from Asia. The textile industry has always migrated to cheaper locations, and always will. When China gets to expensive it will migrate other even cheaper places such as perhaps one day Cambodia, North Korea or West Africa.
When the textile industry has migrated to Asia, the focus shifted from a comprehensive ecological approach as it was at the time discussed in the European industry, involving the finished good (textiles) as well as effluent, to a softer approach only focusing on the textiles, at least the textiles intended for import to the Western markets. For long time nobody in Asia´s textile processing houses really cared about effluents. In Asia, for long time nobody cared about fixation yields of dyes – with commodity dyes there is 3 times as much colour in the effluent compared to state of the art dyes – this was a European discussion. Just in recent years this attitude has started to change, due to pressure of NGOs, retailers who audited their suppliers, and governmental pollution control measures. Today, zero discharge is established in parts of South India, Tiripur region, which is a huge cotton processing center, as a result of governmental pressure, and lack of fresh water.
The situation in major dyes and chemicals manufacturers
The challenge will get harder in the coming years. In the last two years, the three remaining traditional European big dyes & chemicals companies have all announced full exit from production in Europe. Huntsman has announced in 2011 the layoff of 500 of their employees in Switzerland. Clariant shifted production to Asian sites and partly outsourced production. DyStar closed all major German sites and has even closed all their European R&D centers. These changes up are of an epic magnitude, as the chemical industry in Europe has emerged on dyes, and soon no more dyes production would remain in Europe. Along with this goes eventually R&D, process technology and so on. The consequence of this development is clearly that the overall resources and experience would be are drastically reduced once all these epic changes are fully implemented. Of course all these companies have eloquent compliance managers who will claim they have all processes under control and won´t compromise on quality – just recently released sustainability reports underline this judgment. However, the question may be raised, can the still manage this in an ever more complex environment with less and unexperienced people, out of Asia ? They are all playing the marketing card and try to differentiate against competitors, but can they really deliver in the future ?
DyStar is now owned by a Chinese Indian joint venture, Kiri-Lonsen, who are the biggest manufactures of commodity disperse (Lonsen) and reactive (Kiri) dyes in the world, who had in recent years not really gained the reputation of being the eco compliance leader in the industry. At the same time when sustainability reports are released by their subsidiary DyStar, they sell huge amounts of cheap commodity products at rock bottom low prices out of their mass scale manufacturing in China and India.
With the loss of market shares of the traditional chemical companies, serious players with very lean structures, Indian, Chinese and Korean players, have strongly entered the market, and will constantly increase their market shares. Many of them do not have the experience so far to address all the issues related with eco compliance for the thousands of products used in the textile industry. But some companies have developed in a remarkable way which gives some hope for the future at least.
Today´s world is already complex enough – resources are getting critically depleted – not only in the environment – but also in skilled capable expertise in the industry. Moreover, there are additional risks unknown to the public, and more critical issues ahead.
To translate from previous textile to a comprehensive environmental approach as in the Greenpeace detox campaign is of high complexity, but worth the effort.
Testing of chemicals, textiles, effluents and comprehensive databases to support are essential, without intelligent checkpoints and stringent control it won´t work.
Independent Testing and the involvement of independent experts is vital.
Still my concern is, unless world class retailers enforce the vision and blacklist suppliers or even impose draconic penalties in case of non compliance, nobody in the processing chain would really change.
The concept must be beyond a nice marketing tool for the businesses involved. It must be real.
All these obstacles and challenges are huge, yet the target is worth the effort, in the interest of a better future.
The Greenpeace detox campaign of zero discharge of hazardous substances is a challenging endeavor that deserves full support by all serious industry participants.
[ii] p-chloroaniline (“PCA”) is an aromatic amine classified as MAK III A2 which means it is considered as cancerogenic in animal studies. Information on PCA, more
[iii] German patent application DE 19540544 (Hoechst AG, 1995)
[iv] Supplier specification of parabase is usually “< 500 ppm”, e.g. Alibaba Parabase, 2nd supplier Parabase
[v] Technically speaking it is coupled in azo coupling reaction, and no longer detectable as PCA. However, subsequently reduction may release again PCA. on the textile fabrics it is only an issue in case of double anchor reactive dyes such as Reactive Black 5, since in case of mono anchor dyes the PCA part of the dye would not fix and be released with the effluent at the textile processor.
[vi]No MAK amines generated by reductive cleavage according to EU Directive 2002/61/EEC, respectively the19th amendment of the European Limitations Directive 76/769/EEC, lately adopted to Annex XVII of the REACh regulation
[x] Seveso-dioxine is 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
[xi] Ökotest CD 92-96, Sonderheft Kleinkinder 95-pg 133: “Kinder, die in Secondhand-Kleidung aufwachsen, sind möglicherweise gesünder als solche, die ständig nach dem letzten Schrei gekleidet sind”,
[xii] Dr.med H. Bresser: Kleiderallergie
[xiv] Greenpeace report 2005 ,”Dioxine und Dioxin-ähnliche Substanzen in den Chemiemülldeponien der Basler chemischen Industrie” , Forter report, page 36
[xv] Publication in peer reviewed journal of extended study in preparation
[xvi] Information on Aniline, aniline hazard summary
[xvii] 1.Uni Bayreuth, 2.Wikipedia information, 3.The history of indigo : www.unb.ca/fredericton/science/chem/outreach/…/Indigo.pdf
[xix] Indigo purification patent by BASF: „Verfahren zur Reinigung von Indigo“, EP0509274 A1