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CLAUDIO
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Posted: 27 June 2011 at 11:53am | IP Logged Quote CLAUDIO

Last year TCMTB was a problem in Argentina:

AAQTIC organized:

 ROUND TABLE: SOME ASPECTS OF THE CURRENT PROBLEM OF TANNING EFFLUENTS
Panelists: Eng. Martín Gelaf; Eng. María Inés Iribarne; Eng. Jorge Garda; Dr. Horacio González; Dr. Carlos Gotelli

Moderator: Lic. Patricia  Casey
This round table deals with the problems occurring in 2010, when cyanide concentration values in effluents from tanneries turned out to be higher than permitted.
There was a review of cyanide types, of the test techniques employed, of any possible interference, of products employed in tannery that may have a positive response, and the operations that may cause cyanide to occur in effluents.

Power pont (spanish):http://www.aaqtic.org.ar/jornadaIII/index.html

Best Regards

 

 

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Elton
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Posted: 27 June 2011 at 3:03pm | IP Logged Quote Elton

Good questions.  Allow me to address a few questions:

1.  TCMTB is not banned by any national authority. 

2.  TCMTB has approval for use in even the most highly regulated countries.  In fact, it is the only active substance registered in some very restrictive countries. 

3.  TCMTB has come under question by some NGO or eco-label organizations - no surprise as they are concerned with ALL chemicals in leather and TCMTB just happens to be the most widely used fungicide.  When provided with appropriate data these NGO's have approved the use of TCMTB at equal or higher levels than other fungicides under review.  Note that the supportive toxicological and environmental fate data is typically the intellectual property of commercial companies and not made available in the public domain.  The reason is that this data is very expensive to generate - in the region of $5 million for a new active substance.

4.  Under normal tannery use conditions, cyanide is not generated from TCMTB at any levels of concern. I understand that the use of an inappropriate analytical method is the issue in Argentina and this is being addressed.  (Reference ASTM Standard Methods for the Examination of Water and Wastewater for the correct procedures to be used to eliminate interference in cyanide testing). 

5.  With regard to commercial chemical companies suggesting TCMTB  may be "banned" when these competing companies are trying to generate interest in their own products...  well, imagine that!

 

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seogsoo
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Posted: 28 June 2011 at 3:53am | IP Logged Quote seogsoo

Thank you so much. It is very clear now. One more thing.......I can read Korean, English, Chinese, Japanese....But I am regrecting that "Why I haven't learn Sapnish?"
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CLAUDIO
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Posted: 28 June 2011 at 12:31pm | IP Logged Quote CLAUDIO

At this point, we are finishing an article for “Tecnologia del Cuero”, the magazine of AAQTIC, based on the filming of the round table, (in spanish of course).

In about a month, we will be happy to prepare an extended abstract in english, for all to read.

Best regards

 

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seogsoo
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Posted: 28 June 2011 at 9:22pm | IP Logged Quote seogsoo

Mucho Gracias. If possible, I would like to have a copy as well
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kallenwe
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Posted: 29 June 2011 at 9:03am | IP Logged Quote kallenwe

Thank you Elton and Claudio, we really appreciate the references and real story from the hores's mouth. 

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CLAUDIO
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Posted: 22 July 2011 at 1:36pm | IP Logged Quote CLAUDIO

 

AAQTIC PUBLISHED REPORT ON CYANIDE IN EFFLUENTS

 

  AAQTIC, Argentine Leather Industry Chemists and Technicians Association, has published a new report on Cyanide in effluents on its website. This report is available in both English and Spanish.

 

Summary:

CYANIDE IN EFFLUENTS

Round Table: SOME ASPECTS OF THE CURRENT PROBLEM OF TANNING EFFLUENTS

Held at the 3rd National Technical Symposium of the Tanning Industry - November 26, 2010. Paseo La Plaza, Buenos Aires.

 

Moderator:

·       Lic. Patricia Casey (Quality Manager at Curtiembres Fonseca and Vice President of AAQTIC’s Board)

 

Panelists:

·       Eng. Maria Inés Iribarne (Environment Manager at Curtiembre Hispano Argentina)

·       Dr. Carlos Gotelli (Member of the National Academy of Pharmacy and Biochemistry -Academia Nacional de Farmacia y Bioquímica-; Member of the New York Academy of Sciences; Director of the National Center for Toxicological Research; and Consultant at the World Health Organization regarding heavy metals)

·       Lic Horacio González (Business Manager at Buckman)

·       Eng. Jorge  Garda (Environment Manager at Curtiembres Fonseca)

·       Eng. Martín Gelaf (Technical Director at Curtiembre Hispano Argentina)

Main speaker: Eng. Martín Gelaf

Summary

The main purpose of the presentation is to show the findings made on an issue that worried the tanning industry in Argentina throughout 2010: the detection of cyanide in effluents from several tanneries. 

Cyanide concentration values in tanning effluents have been measured and they turned out to be higher than the permitted 1 mg/l (1 ppm) according to the Standard Method (20th Edition) for total cyanide or 0.1mg/l of cyanide destructible by chlorination according to the Standard Method CN 4500 (paragraphs C and E). As a result, penalties such as closures have been applied.

 

This situation has no precedents in the national and international tanning industry and, to confirm it, some local authorities have been consulted and the opinion of foreign consultants has also been considered.

In view of such reality and knowing that tanners do not use cyanide in products for their processes, it has been decided that different alternatives should be researched on. These alternatives will be shared in this presentation.

It has been established that it is a complex issue, that conclusions are partial, and that further studies must be carried out. The purposes were:

·       To understand the definition of cyanide pursuant to standards.

·       To know how to prepare and preserve the samples to be analyzed.

·       To understand the different laboratory methods to measure cyanide levels and challenge the values obtained and potential interferences that may appear.

·       To analyze which chemical products may generate cyanide under certain special pH and temperature conditions, and presence of oxidants, among others.

There are a lot of doubts with respect to the foregoing issues since the different detection methods produced different cyanide values for the same effluent sample. 

The most controversial chemical product which should be studied further is the use of the TCMTB fungicide (C9H6N2S3) which is the 2-(thiocyanomethyl) benzothiazole.

 

 

One of the manufacturers,  Buckman, has informed that the TCMTB molecule does not generate detectable levels of cyanide under regular conditions of application and treatment of tanning effluents, if the analytical methods are appropriate. The TCMTB chemical formula does not contain a labile cyanide group under industrial use conditions.

TCMTB is a product that decomposes at pH > 10 and temperatures > 120 °C; that is, the cyanide found was generated by the taking and preparation of the sample and the measurement method used.

Despite the remarks based on the need to treat TCMTB as interference in the analyses, many tanneries had to stop using TCMTB in their processes. 

Another important issue is that work should be performed jointly with the Government Instrumentalities to know the adequate detection methods to be used, and to make sure that they are applied by qualified people, in contact with the tanneries’ technical departments.

According to the information gathered in the inspected companies, the method used by the controlling authority is not the one stated by law, and the tests performed show that different methods lead to different results.

Sodium hypochlorite oxidation is the customary method for the elimination of cyanide from industrial effluents where cyanide salts are used (e.g. Electroplating). It has been confirmed that in the case of an effluent treated in the retanning process with limit values of 700 mg/l of DQO and 200mg/l of DBO the addition of sodium hypochlorite has caused an increase in the concentration of cyanide destructible by chlorination detected by laboratory method.

 

 

 

.

For a complete version of the report in Spanish, please click here:

http://www.aaqtic.org.ar/jornadaIII/pdf/cianurov12.pdf

In English, click here

http://aaqtic.org.ar/ingles/pdf/Trad_Ingles_CIANUROV12.pdf

 

The report will be published in “Tecnología del Cuero” magazine.

 

 

 

About AAQTIC

AAQTIC, Argentine Leather Industry Chemists and Technicians Association, is a non-for-profit association founded in 1959 formed by technicians of the tanning industry.

After 50 years, their institutional goals keep being: making Conferences and Courses, as well as other activities in its head office. It has published its magazine, Tecnología del Cuero, since 1960 and organizes Symposia every two years. Besides, it launched its own website, www.aaqtic.org.ar, in 2000.

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DavidR
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Posted: 22 July 2011 at 2:49pm | IP Logged Quote DavidR

Dear Fellow tanners: (advantageous term encompassing
females as well!) The sanitary authorities by fomenting
the non-destruction of keratins, that is hair-saving
processes, supposedly to diminish C.O.D in the effluents
of tanneries at the cost of increasing C.O.D.at the land-
fill disposal sites. Theses types of solutions to
environmental problems are typical of advice from
thermodynamically ignorant "experts" not viewing the
whole picture! The positive oxidation states of of sulfur
have the property of not only oxidizing the negative
(sulphide= minus two left over!)as in the S*S bond but
the C*N triple bond as well. Thus the COD produced by
destruction of sulphides by higher oxidation states of
sulfur in destroyed hair, yield as well non-negative
(including cero,e.i.
elemental sulphur!) species that react with anerobic
naturally formed cyanides as well! Eliminating these
naturally formed keratin decay chemicals such as
sulphites and thiosulphate, there results in more CN-
present in the effluents! Hair saving is akin to self
abuse in the tannery! Often there are complex organic
sulfur containing chemicals that smell like onions that
are a sign of anerobic processes that are associated with
cyanide formation as well(caution with smelling!) and the
immediate emergency solution is to use some sulfite or
metabisulphite to replace the required plus four sulfur
being carted off to the land-fill to generate problems
there instead! Expert sanitary engineers not knowing the
use of thermodynamic reasoning is the result of bad
education, not Elton's biocide!
   Go ahead you s.o.b. sanitary experts! You cannot even
threaten to close my tannery any more!

Edited by DavidR on 22 July 2011 at 2:59pm


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kallenwe
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Posted: 22 July 2011 at 4:25pm | IP Logged Quote kallenwe

Not only can they not close your tannery, they can not close about 1000 other tanneries that all have closed their doors.  Local governments love to entice tanners to open plants only to turn on them once vested to "collect" more revenue.  One of the easiest ways to do that is claim "toxic" waste issues.  Of course the tannery smells bad, only hires hard working people (low class people who actually sweat and earn their pay), and looks dirty,  so all the fancy folks prefer to move them out away from "good", civilized folks.  Take their money and dress up in that fancy leather, but don't associate with those "polluters." 

Notice bacteria and natural sources were not mentioned.  They have no money.  To get funded (ie global warming, fear mongering, etc.) you must prove the people with money need to give some to you.  Or maybe their competition or enemies, etc. 

Although someone with an axe to grind may also tend to slant the story.  However, none of us is without bias of some sort, and there is great value in presenting more than one viewpoint. 



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DavidR
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Posted: 23 July 2011 at 9:54pm | IP Logged Quote DavidR

Perhaps I did not make myself clear: By hair-saving
procedures one eliminates the extensive formation of plus
oxidation sulfur chemicals such as Sulfite and
Thiosulfate that are products of keratin destruction that
react with NATURAL formed CN- (cyanide anion) resulting
from anaerobic chemical processes not intended nor
required or even known, by the tanner! These hair saving
techniques should have never been allowed to be implanted
by "request" of sanitary authorities feeling their oats!
The parallel formation of organic volatile sulfur
compounds that smell like onions are just a symptom of
these undesired reactions caused for lack of sulfur
species of plus oxidation states not being present
because they were stupidly sent to a land-fill! The
abuse of caustic soda, in hair saving systems, ruins more
leather than any one other single cause!
The resistance to cyanide poisoning by such scavangers as
buzzards, so common in the Latin American scene, is
nature's way of dealing with alkaline anerobic formation
of Cyanide that is very naturally formed from waste
proteins! The sheer idiocy of blaming Elton's fungicide
because one can easily point a finger at Buckman! The
antidote for cyanide poisoning in acid based digestive
systems (buzzards have an alkaline digestive system!) is
simple thiosulfate, preferably blood-injected to get it
to the brain and nervous tissue quickly! Nature uses
"naturally-produced" cyanides ("prussic" acid= bitter
almond taste!) to protect itself, and I have heard of
cyanide intoxications of girls eating too many peach-pits
while making jam! Juca Root (Mandioc) of the Tapioca
Family, needs to be double boiled, the last boil with
lemon or sour orange preferably in acid, to avoid death
by natives in South America consuming it! There is so
much cyanide present that it smells like bitter almonds
and nematodes (worms in dirt) will not attack the plant,
hence it is a starch crop that is "self-fumigated"
against insect pests, very "naturally", but can be deadly
to the uninformed.

Edited by DavidR on 23 July 2011 at 10:33pm


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