• Textile floorcoverings are always manufactured in compliance with the ban on the use of certain substances

 
• Certain hazardous substances specified in the GUT criteria must not be identified by the pollutant test

 

The GUT criteria must be complied with already when carpet material is manufactured. Thus, textile floorcoverings must always be manufactured without the following substances being used:

• certain carriers
 
• azo dyes having a carcinogenic component
 
• highly volatile chlorofluorocarbons (CFCs)
 
• Dyes and pigments containing the listed heavy metals as ingredients of the dyeing component must not be used to dye the pile material:
  
  lead (Pb), cadmium (Cd), mercury (Hg) or chromium  (chromium total) or Cr(VI)
  
  The limit value for the total heavy metal content of a fitted carpet is 100 mg/kg.
  
 
• ZDEC (zinc diethyl dithiocarbamate) as a vulcanisation accelerator for lattices

 

In special test procedures, GUT has independent test institutes test the materials to be tested for the following hazardous substances and classes of substances:
 

Since 1 January 1995 textile floorcoverings having a share of wool have had to comply with the specifications indicated hereinafter:

• Basically, only such articles having a share of wool can be awarded the GUT Signet as have been mothproofed.

 
• At present, permissible mothproofing agents are agents containing the active substances permethrin or sulcofuron.

 
• The permissible methods of application are:
• dye-bath application,
• continue process,
• foam application,
• spray application according to the autoclave process, if a fastness of 0.5 can be shown in compliance with IWS TM-28.

 
• New material must adhere to the following maximum quantities:

• The following information must be included in the product description:

This method identifies the free and the salt-linked PCP in the material to be analysed.
Conduct a hot extraction of the analytical sample (5g); subsequently add internal standard and convert with acetic anhydride as acetate. Use a silica gel cartridge to carry out the necessary purification of the extract. Measure the analytical parameters by means of gas chromatography and carry out detection by means of the electron capture detector (ECD). Assure the quality of the analytical result regarding yield and preparation by adding tetrachlorophenol standards.

Identification limit: 0.1 mg/kg ( = 100 µg/kg) relative to the original sample

Like in the case of the identification of the volatile organic compounds, identify formaldehyde and other aldehydes and ketones in an emission test chamber in analogy with the measurement for volatile organic compounds (VOC). Enrich the formaldehyde on suitable adsorber materials (e.g., DNPH cartridges); then conduct elution and subsequently identification by means of HPLC.

The identification limit for textile floorcoverings resulting from this method is currently 10µg/m3.

This method identifies all relevant pesticides (see table above) from natural fibres such as sheep wool, cotton, animal mixtures, …) that are used in textile floorcoverings as upper-side finishing materials.
For this purpose, extract a 2g fitted-carpet sample in an ultrasonic bath with a mixture of hexane/ dichloromethane (85/15). Clean up the extract through acetonitrile shaking or adsorption chromatography over Florisil. Measure and quantify by means of gas chromatography through detection at the electron capture detector (ECD).

The identification limit per component resulting from this method is 40 µg/kg.

Vinylchloride is identified according to the test-chamber process in analogy with VOC.

Identification limit: 0,1µg/m³

Vinylacetate is identified according to the test-chamber process in analogy with VOC.

Identification limit: 2 µg/m3
Monomer from EVA dispersions, etc.

This analytical method is designed to identify benzyl and ethyl accelerators in the foam backing of textile floorcoverings and similar products.
Comminute 10g of the latex foam backing to be tested, extract with ethanol, adjust to a defined volume, and develop by means of thin-layer chromatography on normal phase by dyeing with aqueous copper sulphate solution.
In order to evaluate, compare with the standard components.
The GUT requirements ban the use of ethyl accelerators during production.

This method is designed to identify carcinogenic aromatic amines and their azo dyes in fitted carpets or other textiles.
Use the pile material of a carpet sample. (In case of multi-coloured surfaces and objects consisting of different textile parts, test the various parts separately.)
Comminute the textile sample, split it into the various colours and analyse. Digest the sample at 70°C by means of citrate sodium hydroxide buffer solution, and subsequently carry out the reductive cleavage of the amines with sodium-dithionite solution. Purify the resulting solution over extrelute and elute the analytical parameters by means of tertiary butyl-methyl-ether. Determine the analytical parameters by means of liquid  chromatography and detection at the diode array detector (DAD).

The identification limit is at 5 mg/kg of sample.

Carriers are used as special adjuvants to dye polyester fibres in order to achieve quicker diffusion of the dyes into the fibre and increased dyestuff absorption. However, polyester fibres are not generally used as pile material for textile floorcoverings because they do not meet the demands placed on quality. In tufted fitted carpets, polyester fibres are used as fleeces, which are then used undyed.

All azo dyes have the general formula R1-N=N-R2, it being possible that the two remainders are either identical or different.
Azo dyes are suited for the dyeing of various substrates such as synthetic and natural textile fibres, leather, paper, mineral oils and waxes.
Azo dyes originate from the coupling of diazotised aryl-amines with suitable coupling components. Through reductive cleavage, e.g., through chemical reduction agents or also intestinal bacteria, aromatic amines – some of which are carcinogenic – may, however, be released again.
Under the Ordinance on Articles of Daily Use and EU Directive 76/769/EWG, such azo dyes in textile and leather products (these include carpets) as may release carcinogenic amines and may come in direct and prolonged contact with the human skin or oral cavity must neither be used nor marketed.

GUT banned the sue of these azo dyes already long before legal provisions were passed.
 

CAS-number	EG-number	Name of substance
92-67-1	202-177-1	4-aminobiphenyl
92-87-5	202-199-1	benzidine
95-69-2	202-441-6	4-chlorine-o-toluidine
91-59-8	202-080-4	2-naphthylamine
97-56-3	202-591-2	o-amino-azo-toluene
99-55-8	202-765-8	5-nitro-o-toluidine
106-47-8	203-401-0	4-chloroaniline
615-05-4	210-406-1	4-methoxy-m-phenylendiamine
101-77-9	202-974-4	4,4‘-methylene-dianiline
91-94-1	202-109-0	3,3‘-dichlorobenzidine
119-90-4	204-355-4	o-dianisidine
119-93-7	204-358-0	3,3‘-dimethylbenzidine
838-88-0	212-658-8	4,4‘-methylendi-o-toluidine
120-71-8	204-419-1	p-cresidine
101-14-4	202-918-9	4,4‘-methylen-bis-(2-chloroaniline)
101-80-4	202-977-0	4,4‘-oxydianiline
139-65-1	205-370-9	4,4‘-thiodianiline
95-53-4	202-429-0	o-toluidine
95-80-7	202-453-1	4-methyl-m-phenylene-diamine
137-17-7	205-282-0	2,4,5-trimethylaniline
90-04-0	201-963-1	o-anisidine
		6-amino-2-ethoxynaphthalene *
399-95-1		4-amino-3-fluorophenol *
60-09-3	200-435-6	4-amino-azo-benzene *

* TRGS 614 of May 1999 covering restrictions on the use of azo dyes also provides for a ban on the use of azo dyes that may be split up into carcinogenic aromatic amines.
 

Properties
CFCs are aliphatic and cycloaliphatic carbon compounds that are either completely or incompletely substituted by chlorine and/or fluorine. Some also contain bromine (halones).
CFCs are chemically stable, inseparable, non-explosive, odourless and tasteless gases that are largely non-toxic for humans, animals and plants.
Due to their chemical stability they feature difficult degradability and a long life in the environment.

Use
They are used as coolants for refrigerators and deepfreezers, heat pumps and air-conditioning systems, as foaming agents for plastic materials, as chemical cleaning agents and as propellants.

National and international activities
Through their high stability and inertness, CFCs get as far as into the stratosphere. There they cause damage to the ozone layer and reinforce the greenhouse effect.
In 1985, the United Nations signed a convention for the protection of the ozone layer in Vienna. By 1987, at least some of the member states agreed upon first concrete measures in the Montreal Protocol. The protocol provided for a 50% reduction of the production and consumption of CFCs by the year 2000. When it became quickly clear that this reduction would not be sufficient, the Montreal resolutions were tightened in 1990 (London), in 1992 (Copenhagen), in 1995 (Vienna), in 1997 (Kyoto) and in 1999 (Beijing). The new EU directive on substances leading to a reduction of the ozone layer became effective on 1 October 2000. In this directive, some of the periods specified in the Montreal Protocol were rescheduled to earlier dates and intermediate steps were specified. For example, the use of fully halogenated CFCs and halones is banned for good. (with some exceptions)

In Germany, production and use were provided for in 1991 in the Ordinance banning the Use of CFCs and Halones. This ordinance provides for reduction of the ozone-layer-related destructive potential through step-by-step introduction of less harmful substitutes. Announcement of a substitute went along with a ban on the use of the original substance, older facilities benefiting from transitional periods. Thus, the production of halones was stopped almost completely in Germany as early as in 1992 and that of CFCs in 1995.

The foam backings of textile floorcoverings are made by mechanically working air into the SBR latex compounds. In contrast to what is often falsely claimed, no CFCs are used for the purpose.
 

Dyes or textile adjuvants used to colour textile floorcoverings may contain heavy metals in the form of metal salts or metal oxides. Furthermore, the printers often use dyes that, for colouring, may contain heavy metals in the molecule, the so-called metal complex dyes.
After the respective dyeing process, the of the dyeing chemicals is washed out and, in this manner, gets into the waste water. GUT has banned the use of dyes and pigments containing the heavy metals lead (Pb), cadmium (Cd), mercury (Hg) and chromium (Chromium total or Cr(VI) as ingredients of the dyeing component of the pile material, because these have toxic and / or carcinogenic properties. The limit value for the heavy metal content of a fitted carpet is 100 mg/kg.
The harmful effect of heavy metals is primarily based on the deactivation of enzymes, on changes in the permeability of cell membranes as well as on chronic, mutagenic and carcinogenic effects.
 
 

Lead

Lead and its compounds count among the substances having a strong toxic effect on the environment.
In the sector of water pollution, for example, the lead pollution in sewage treatment plants originates from what is washed off streets and roofs. Like other heavy metals, lead accumulates in sewage sludge, in sediments and also in living organisms.
Sources of lead are metallic lead (water supply pipes, soft solder), lead oxides such as litharge and minium (glass and varnish production, paints) as well as lead cyanamide (rust-proofing agents). Lead silicates are contained in lead crystal glass and in the glazes of earthenware. Besides, there is still a small portion of fuel that is leaded. In present-day paints, the share of lead is under 1%.

Toxicity
Chronic lead intoxications have toxic effects above all on the nervous system, the blood formation and probably on the kidneys. Already low lead levels in the blood (> 10µg Pb/dl) have been proved to permanently reduce the intelligence quotient in children. Lead oxide (PbO), lead carbonate, lead sulphate and organic lead compounds cause a greater danger than metallic lead. It has as yet not been clarified whether in Germany lead pollution of the environment poses a serious threat to the population, in particular to children. On the whole, lead pollution in Germany has decreased in the last few years.
 
 

Chromium

Chromium is a fairly frequent element and occurs in the earth’s crust in an average concentration of 200 mg/kg. In the soil, usually 10 to 90 mg/kg is found. Chromium and its compounds have a variety of uses in the crafts and in industry as mordants, oxidisers, etchants and dyes as well as alloy components, as catalytic agents, for wood impregnation, and as tanning agents for leather processing. In the electroplating industry, chromium is used to plate metal surfaces.
Trivalent chromium is an essential trace element for humans and animals. Sexivalent chromium compounds cause allergic and asthmatic reactions and are considered to be carcinogenic. Chromium and chromium compounds reach surface waters primarily through the waste waters of the chromium-processing industry, of electroplating plants and tanneries.
In water, chromium occurs in trivalent and sexivalent form. Under aerobic conditions, chromium(VI) is stable. Under anaerobic conditions, it is reduced to chromium(III). Under oxidising conditions, conversion of chromium(III) into chromium(VI) is also possible. Owing to the formation of hardly soluble chromium(III) compounds and the adsorptions of chromium to suspended matter, a large part of the chromium is bonded in particles.

Toxicity
Only the trivalent and sexivalent compounds of chromium have toxicological significance, the trivalent compounds having a strongly sensitising effect and the sexivalent ones having the greater toxicity. When inhaled by humans, CrVI compounds can possibly cause cancer. Most sexivalent compounds of chromium in the form of breathable dusts are classified as pollutants suspected of having a carcinogenic effect in humans (category IIIA2).
 
 

Cadmium

Cadmium is used as an anti-corrosive, as a component of batteries, accumulators, solar cells, as a paint pigment for ceramic and plastic products and finally as a stabiliser of plastic materials (PVC). Moreover, cadmium occurs during the smelting of zinc ores.
After restrictions on the use of cadmium had been imposed, the consumption of cadmium as paint pigments and as stabilisers in plastics manufacture declined substantially. With about 600 t/a, cadmium use in NiCd accumulators accounts for the overwhelming share of cadmium consumption in Germany. Via the food chain, cadmium enriches in aquatic organisms and, when consumed, also in the human body. 6% of the cadmium taken in via the food gets into the human body, only some of the cadmium is excreted again (accumulation). Permanent exposure to cadmium may lead to renal damage and – under certain conditions – also to changes in the bone-structure. Higher cadmium concentrations have a growth-inhibiting effect on aquatic organisms. Cadmium salts have a very harmful effect on water and already very small concentrations have an intoxicating effect on the environment. Under the Law on Waste Water Levies, the emission of cadmium into waters is subject to payment of a levy. Again and again, fairly high cadmium concentrations are found in vegetables, edible mushroom, and above all in the entrails of fatstock.

Toxicity
The carcinogenic effect on humans has as yet not be proven definitively and appears to originate from inhaled cadmium rather than from orally administered cadmium.
Cadmium and its compounds, taken in orally or dermally, are moderately toxic (in particular nephrotoxic) and, when inhaled, have a certain carcinogenic potential. Therefore, exposure to cadmium should be minimised, e.g., through proper disposal of waste materials containing cadmium (paints, plastics, batteries and photo elements).
 
 

Mercury

Metallic mercury is used in thermometers, manometers, mercury discharge lamps and special batteries as well as in extractive metallurgy. Organic an inorganic mercury compounds are used as fungicides and insecticides, as seed, wood and animal-hair protectants. Finally, mercury is used in amalgams for dental caries treatment.

Toxicity
Mercury is a ubiquitous environmental poison. The environmental pollution is largely of an anthropogenic origin. Normally, mercury is taken in mainly via the food, in particular via fish. In humans with many stoppings, up to 50% of the daily intake can come from mercury amalgam. Here – as in the case of mercury supply via the food – no pathogenic concentrations are reached.
The toxic effect of mercury is based primarily on the SH group blockade of enzymes and other proteins. Toxicity increases from monovalent inorganic mercury through divalent mercury to inorganically linked mercury.

MAK list:
0.1 mg/m3 (elementary mercury)
0.01 mg/m3 (organic Hg compounds) methyl mercury classified as ”clearly teratogenic” (category A).

For reasons of workplace safety and environmental protection, the Ordinance on Dangerous Substances prohibits the marketing and the use of mercury compounds in anti-fouling paints, for wood protection, for impregnation of heavy industrial textiles and for water conditioning.
 

During the production process, the accelerator types on the basis of zinc-diethyl-dithiocarbamate used for the vulcanisation of foam backings decompose into the relevant secondary amine. Together with the ubiquitous quantities of nitrogen oxides (Nox), this amine may react into the carcinogenic N-nitrosodiethylamine. For reasons of workplace safety, this led to the specification of limit values for various industrial sectors (rubber-processing industry, etc.). To ensure the safety of production workers and also of final consumers, GUT firms have not used ZDEC for the manufacture of foam-backed textile floorcoverings since 1991. Instead, the ZDEC that is unable to form carcinogenic N-nitrosamines is used. Since 1991, this ban has been monitored by GUT’s contractual institutes, and each violation has been severely punished by GUT.
 

Caused by the discussion about formaldehyde and its possible occurrence in textile floorcoverings, PCP was in some cases used in the 80s to stabilise SBR lattices. Due to its excellent effect, PCP was used in the form of the Na salt or as PCP ester in order to stabilise the SBR latex and thus to protect it against mouldiness. When it became known that PCP was used in this manner, GUT announced a comprehensive ban on PCP use, which is monitored by means of GUT’s own analytical process.

Properties
As a compound of the chlorophenols, pentachlorophenol (C6Cl5OH)counts among the chlorinated hydrocarbons. Under normal conditions, PCP forms odourless, white, needle-shaped crystals that are almost insoluble in water and are soluble in lyes, alcohol, ether and acetone.

Use and consumption
PCP is used as an active substance in algicides, fungicides, disinfectants, in leather protection and as a preservative agent. The best known and most popular use in Germany was its earlier use in wood preservatives.
Further areas of use include cotton production, the paper industry, the textile industry and the manufacture of adhesives and glues, as well as disperse paints and oil paints.
The information about worldwide annual production quantities fluctuate between 25,000 t and 90,000 t per year (1991). In 1995, the PCP production in Germany still exceeded 1,000 t.

Occurrence in the environment
Pentachlorophenol occurs everywhere in the environment, so that every human is necessarily exposed to it. The following list gives examples of the widespread occurrence of PCP in a variety of materials.
 

Occurrence	PCP-content
PCP-treated pine wood (USA)	1400-10.400 mg/kg
Textiles in air containing PCP (laboratory test)	4-11 mg/kg
Upholstering material	2,4-11,3 mg/kg
Curtains	3,0-5,2 mg/kg
Fitted natural-fibre carpets (presumably impregnated)	80-120 mg/kg
Carpet (14 years after use of wood preservatives containing PCP)	10 mg/kg
House dust (basic exposure without wood preservatives)	ca. 1-5 mg/kg
House dust (14 years after use of wood preservatives containing PCP)	28 mg/kg
Cast	0,5-23 mg/kg
Wallpaper	10-14 mg/kg
Wood ash	2-5 µg/kg
Ash from waste incineration plant	12-90 µg/kg

   (From: Rippen: Handbuch Umweltchemikalien 1990)

The most frequently discussed PCP source is wood preservatives. 

Intake by humans
Humans take in PCP via their respiration (as vapour or dust-linked), via their food and via the skin (from clothing and contact with other articles of daily use). In case of all three intake ways, the target organs in the human body are essentially the liver and the kidney.As much of the PCP taken in is excreted via the urine, the concentration determined there is a good measure for the average exposure to PCP. The usual values, which are shown also by people having no contact with wood preservatives, amount to about 10 µg/l.

Acute toxicity
In the case of PCP intoxications, the following symptoms are described: dizziness, headache, nausea, respiratory distress, accelerated respiration, profuse perspiration and increased body temperature.
The acutely lethal dose for humans is estimated to be about 30 mg of PCP/kg.

Long-term effects
Animal experiments revealed correlations of chronic effects. For example, long-term tests with mice that had been administered technical PCP over a period of two years, in addition to other effects, showed a clearly carcinogenic effect of PCP.

According to animal experiments, pentachlorophenol moreover has a weakly chromosome damaging effect. An slightly increased number of chromosome disjunctions in lymphocytes was found in wood-preserving workers.

Risk assessment
As the carcinogenic effect of PCP was clearly shown in animal experiments, the senate commission for the testing of hazardous work materials has not specified a MAK value (maximum workplace concentration) or a BAT value (biological work material tolerance value) below which there is no health impairment. Therefore, the MAK list classifies PCP in category III A 2 (substances as have turned out in animal experiments to be clearly carcinogenic).

On the basis of the long-term animal experiments, the Federal Health Office made a health-related assessment of the PCP room-air concentrations. The so-called NOAEL value amounts to 3 mg/kg of bodyweight/day. This is the value below which no negative effects can be determined. This value is divided by a high safety factor of 1000, which results in the so-called ADI value of 3 µg/kg of bodyweight/day. This is the value of the tolerable daily intake, which is thus 180 µg in a 60 kg person.

From this, the Federal Health Office – based on the respiratory volume and a permissible 10% utilisation of the ADI value – calculated a tolerable room-air concentration of 1 µg PCP/m3 of air. If this value, which has been recommended under the aspect of prevention, is complied with, any health impairment whatever can be ruled out.

Legal foundation
In 1989, the federal government passed an ordinance banning pentachlorophenol on the basis of the Law on Chemicals. Therefore the manufacture, the marketing an the use of PCP, Na-PCP products and products containing more than 5 mg/kg of PCP was banned. Exceptions from this ordinance may be admitted if the PCP occurs during the synthesis of other substances, if it is used for scientific purposes only, or if it is to be disposed of.

The remaining quantities are those that were emitted into the environment before the ordinance came into force and that are still being produced abroad today.
 

Properties
In an uncombined form, formaldehyde (HCHO) is a gas that has a pungent smell, is colourless and chemically highly reactive; its smell is still perceived in concentrations under 1 ml/m3. In polar solvents such as water and alcohol it is readily soluble. An aqueous solution of about 30-40% is known as formaline.

Occurrence and use
In nature, formaldehyde is formed, for example, as an intermediate metabolic product in the cells of mammals and during photo-oxidation in the atmosphere.
Formaldehyde is regarded as one of the most important organic elements in the chemical industry. Formaldehyde production and consumption keeps rising up to the present day; from 500,000 t in 1984 through 750,000 t in 1995 to 853,586 tons in 1998.
In industry, formaldehyde is used in the production of chip boards, synthetic resin, dyes, fitted carpets and textiles and also as a disinfectant and preservative agent. The following table gives a survey of the diversified possibilities for use of formaldehyde.
 

Formaldehyde
plus urea, melamine, and others	plus phenol, resorcine, and others	plus ammonia	plus various substances
aminoplasts	phenoplasts	hexamethylene-tetramine	sundry products
adhesives	adhesives	hardening additives	special adhesives
paper resins	moulded laminates	vulcanising additives	varnish adjuvants
varnish resins	varnish resins	fillers	foams
press masses	press masses	medicaments	artificial horn
foams	foams	fungicides	dyes
textile adjuvants	cast resins	explosives	emulgators
fertilisers	moulding-sand binder	preservatives	solvents
preservatives	abrasives		solutisers
moulding-sand binder	tanning agents
Ion exchanger

(From: Federal Ministry for Youth, Health and Family, 1984)

Emanating as gas from various materials such as wooden materials, floorcoverings, textiles and others, formaldehyde plays an important role in the pollution of indoor-room air.
Formaldehyde reaches the indoor-room air through continuous release in particular through chip boards and products made of them, fitted carpets and insulating foams (urea formaldehyde resins for heat insulation). Here, concentrations exceeding the limit value of 0.1 ppm recommended for indoor rooms by the Federal Health Office may occur.

Intake by humans
Harmful effects of formaldehyde on humans may be either of a toxic or of an allergenic nature. Possible intake routes into the body include the respiratory tract, the gastrointestinal tract or the skin surface.

Respiratory tract
In small concentrations, formaldehyde leads to irritations of the eyes and the airways; in higher concentrations it causes prolonged, reversible and finally irreversible damage to the organs exposed to formaldehyde. 
The following table shows the effects of formaldehyde subject to the concentration of the gas in the air.
 

ml/m3	Manifestations
0,05 - 1,0	odour threshold
0,01 - 1,6	threshold for eye irritation
0,08 - 1,6	threshold for eye and nose irritation
0,5	threshold for larynx irritation
2 - 3	shooting pain in nose, eyes and the posterior part of the pharynx
4 - 5	intolerable for 30 minutes, increasing discomfort and tear flow
10 - 20	strong tear flow after a few minutes continuing for up to 1 hour after exposition, immediately dyspnoea (respiratory distress), coughing, burning in the nose, throat
30	anger to life, toxic oedema of the lungs, pneumonia

Gastrointestinal tract
After oral intake of small doses, it comes to damage to the mucous membranes of the gastrointestinal tract in the form of inflammations, coagulation necroses (protein coagulation due to the formaldehyde effect) and ulcerations (development of an ulcer). The lethal dose for adults is about 10-30g of a 35% solution.

Genotoxicity and carcinogenicity
The toxicity of formaldehyde is based primarily on local effects through direct contact with the tissue. Formaldehyde can react with amino groups of proteins and nuclein acids (DNA) and cross-link them.
Cross-linking with nuclein acids is suspected of causing mutagenic effects. This is the reason why formaldehyde is classified as a weak, directly effective mutagen. It must however be mentioned that these mutagenic effects could not be shown in mammals.
Animal tests with rats have proved formaldehyde to have a carcinogenic effect. However, this can be shown only with high concentrations >= 6 ml/m3.

In the 2001 list of MAK values, is classified in category 4 of the carcinogenic substances.

Contact with the skin
Formaldehyde is classified as a contact allergen, i.e., skin contact may lead to sensitisation. Renewed contact will then cause an allergic contact eczema. In this reaction, the cross-linking of formaldehyde with skin proteins play a major role.

Indoor rooms
On the basis of the earlier MAK value of 1 ml/m3, the former Federal Health Office recommended a standard value of 0.1 ml/m3 for indoor rooms (including residential rooms) as early as in 1977. This value was specified with a view to preventing mucous-membrane irritations and molestations and without taking into account the carcinogenic or mutagenic potentials.
.
Legal provisions for formaldehyde in textiles
Clothing textiles are articles of daily use in terms of §5 para 1.6 of the Law on Foodstuffs and Articles of Daily Use (LMBG). According to said law, it is forbidden to manufacture or treat articles of daily use in such a manner that, if used properly and in a foreseeable manner, they are suited to be harmful to health through toxicologically active substances.
According to Appendix I No. 2.6.2.2. of the Ordinance on Dangerous Substances, to provide textiles which, if used properly, get in contact with the skin and contain more than 0.15% of free formaldehyde with the following marking:

”Contains formaldehyde. For better skin tolerance, you are advised to wash the garment before you first wear it.”

Manufacturers are themselves responsible for complying with the legal provisions, the monitoring duty lies with the federal districts and is there pursued by the chemical inspection authorities for foodstuffs. At present, the legislator requires neither admission nor registration of such articles of daily use.
 

Risk assessment
As a result of the use of resins with small p shares and changes in the finishing process itself, it has, of late, hardly been possible to identify formaldehyde in factory-new clothing. 
 

Pesticide is a collective name for all chemical pest destruction agents. The most frequently used pesticides are insecticides, herbicides and fungicides. Many pesticides have undesired side-effects. For example, animal experiments showed as early as in the 1960s that not only natural hormones but also plant substances and chemicals such as DDT and other organic chlorine chemicals may have an influence on the endocrine system. Numerous pesticides were identified as weak oestrogens.
Additionally, these substances are persistent, i.e., they are hardly degradable and, as lipophile substances, they may enrich in the food chain (bio-accumulation). A risk assessment must also take into consideration that there are indications pointing to an additive or over-additive effect of environmental hormones.

Through legislative measures, pesticide residues in the food chain have meanwhile been markedly reduced.
A special law has banned the manufacture, export and import, marketing, purchase and use of DDT since 1972.
Further bans on the use of plant protectants are provided for by the Ordinance on the Use of Plant Protectants of 1988 on the legal basis of the Law on Plant Protection. For example, there is a complete ban on the use of 35 substances (among them lindane, carbaryl, PCP).
 
 

Acetic ethyl ester, better known as vinyl-acetate, is a colourless liquid having a characteristic smell and a molecular weight of 86.09.

CAS No.: 108-05-4
Boiling point 72 °C
Melting point: -93 °C

In the list of MAK values, vinyl-acetate is classified as a carcinogenic work material of category 3B. Furthermore, vinyl-acetate is regarded as jeopardising water, i.e., harmful to aquatic organisms. It is classified in water-jeopardy class 2.

In addition to the manufacture of polyvinyl-acetate, vinyl-acetate is used as a starting product for the manufacture of numerous copolymers that are primarily used as adhesives, as bonding and coating agents. 

In the carpet industry, for example, ethylene-vinyl-acetate-copolymer is used in the form of a dispersion as a finisher for woven materials. 
 

Vinyl-chloride is a colourless and odourless gas, which, in higher concentrations, has a sweetish smell and a narcotic effect; it has a molecular weight of 62.50.
Vinyl-chloride is combustible, easily flammable, heavier than air, and forms explosive vinyl-chloride-air mixtures in the range between 3.6% and 33%.
It is hardly soluble in water and readily soluble in alcohol and ether.

Use
Vinyl-chloride is used almost exclusively as a monomer for the production of polyvinyl-chloride (PVC) and for copolymerisation with acryl and other vinyl monomers. The polymerisates of vinyl-chloride count among the most important thermoplastic materials.
PVC has numerous technical applications. By adding softeners one obtains soft PVC having an elasticity making it suited for the production of leatherette, tubes as well as floorcoverings. To a minor degree, it is also used as a coolant and in organic syntheses.

Limit values
Vinyl-chloride has a carcinogenic effect. In the MAK list of values, it is classified as a carcinogenic work material of category 1, i.e., vinyl-chloride has clearly been identified as a carcinogenic substance. No medically non-hazardous limit value can be specified, because even the smallest vinyl-chloride concentration has a harmful effect. For such substances, TRK values (technical standard concentration) are agreed upon, which, in the case of vinyl-chloride, amount to 2-3 ppm (ml/m3).
In the Ordinance on Dangerous Substances, an alert threshold value of 15 ppm as an hourly average is specified to protect workers’ health.
The odour threshold value amounts to 4,000 ppm, i.e., damage is caused long before the danger can be smelled.

Vinyl-chloride is strongly water-jeopardising (water-jeopardy class 2). 

Toxicity
It has a narcotic effect on the central nervous system and irritates the skin, the lungs and the airways. Acute symptoms include coughing, dizziness and unconsciousness. Long-term effects may be damage to the liver and the central nervous system as well as cancer. The cancer risk through vinyl-chloride in humans has been known already for 25 years. Prolonged influence of high vinyl-chloride concentrations causes a special kind of lung cancer. Vinyl-chloride itself and its degradation products chloroethylene-oxide and chloroacetaldehyde are mutagenic and teratogenic (embryotoxic).
 

Benzene is a colourless, easily movable liquid having a characteristic ”aromatic” odour. The substance is the simplest and best known representative of the aromatic hydrocarbons. Benzene is easily combustible, chemically stable and may be mixed in any proportion with organic solvents. In water it is hardly soluble. Through its high vapour pressure it occurs as a gas in the surrounding air.

The worldwide production of benzene meanwhile amounts to about 34.5 million tons per year (info refers to 1996); the biggest manufacturers are North America, western and eastern Europe. In the Federal Republic of Germany, 2.67 million tons are produced every year.

Use
Benzene is a starting material for a multitude of organic and aromatic compounds such as nitro-benzene and aniline, phenol, styrol, synthetic caoutchouc, insecticides (e.g., lindane, DDT), azo dyes (e.g., aniline black), plastics, synthetic resins and wash-active substances.
Furthermore, benzene is used as a solvent for varnishes, resins, waxes and oils.
In engine fuels (unleaded petrol), it is used as an additive to increase the knock rating.

Spread and occurrence in the environment
In nature, benzene occurs in small concentrations in crude oil. But, amongst others, it may also occur in case of incomplete burning of organic substances, i.e., for example, in the case of heathland or forest fires. Benzene is obtained through distillation of pit coal and petroleum.

The main source of benzene emissions is the motor-vehicle traffic. Via engine exhausts and evaporation from the fuel tank, from carburettors or fuel-injection systems it gets into the air where it enriches on account of its chemical properties. Here, half of the benzene emitted comes directly from the fuel, the other half is formed later during the combustion process. Further sources of benzene emission include storage, transport and reloading of benzene and of products containing benzene. Also when benzene is distributed from the refinery to the filling station and when the petrol tanks of cars are filled are benzene vapours emitted.

Benzene emissions come from firing plants, carbonising plants and fuel stocks. The following table shows the quantities emitted by various emittants. The information is based on extrapolations.
 

Source	benzene emission t/a
Motor vehicles	29.011
Exhaust gas
Passenger cars	21.506
Commercial vehicles	2.520
Bicycles	1.851
Construction industry, agriculture and military	1.250
Evaporation
Emissions Otto engine - passenger cars	1.765
Distribution of Otto fuel
Storage, reloading, transport, filling station	169
Filling motor-vehicle tanks	231
Firing plants	1.150
Industry without firing plants	1.275
Processes
Chemical industry	450
Mineral-oil refineries	170
Carbonising plants	55
Other (casting plants, etc.)	350
Consumption of solvents and laboratory chemicals	250

 Benzene emissions in the Federal Republic of Germany in 1995 (UBA 1997)

For some other, less important emittants such as waste disposal sites and incineration plants, quantities cannot be accurately indicated.

The information about average benzene concentrations in the air fluctuates between 1 and 160 µg/m3 of air. Concentrations of up to several hundred µg per cubic metre of air have been measured in densely populated areas with intense road traffic as well as in the neighbourhood of filling stations. Area-related annual mean values are around 5 µg/m3 in rural areas and 15 µg/m3 in metropolitan areas.

For smokers and passive smokers, an additional source of exposure is the main smoke stream of cigarettes. When a cigarette is burned, 10-100 µg of benzene is released. If 20 cigarettes are smoked per day, the daily intake is estimated to be 400 µg. 

In addition to the air as an enrichment medium, part of the benzene quantities emitted also get into the soil and the water through rain-wash and leakage. Except for local pollution, however, benzene concentrations in the soil are small. The values in well water, underground water and drinking water are under 1 µg/l.
 

Toxicity
Benzene has a central depressory, i.e., a narcotic effect, damages the blood formation in the bone marrow and can cause tumours, an increase in the number of leukaemia cases being prevalent.
When inhaled, benzene vapours have a highly toxic effect. Symptoms include dizziness, nausea, benumbedness and unconsciousness.
Chronic toxicity is characterised by a number of unspecific symptoms such as tiredness, weakness, sleeplessness as well as dizziness, pallidness, flickering eyes and heart throbbing during physical efforts. Chronic intoxications after the intake of minor quantities over a prolonged period will cause damage to the bone marrow, the liver and the kidneys. Benzene can cause leukaemia and is regarded as a highly carcinogenic substance.
In addition to the carcinogenic and chronic effects, benzene also has an acute toxic effect after short-term exposure. A benzene content of 2 % by volume in the air inhaled will cause death after 5-10 minutes.
The liquid may also be absorbed via the skin and, in this way, causes severe intoxications.
It must be assumed that benzene makes a substantial contribution towards the general cancer risk. Moreover, benzene is classified as a substance having a mutagenic potential. 

All general toxic effects usually occur in a range of concentration that is irrelevant for outdoor-air conditions. Thus, the remaining hazardous effect for the general population is the carcinogenic effect. 
 

Limit values, guidelines
Due to its carcinogenic effect, no limit value can be specified for benzene below which a health risk can be ruled out. For the exposure of workplaces, some of which exceed the ”normal” concentrations in the air by a multiple, the senate commission for the testing of hazardous work materials has classified benzene as clearly carcinogenic in category III A 1.

The technical standard concentration (TRK value), which is specified in line with the state of the art and must not be reached, amounts to 8 µg/m3 for carbonising plants, fuel-filling stations as well as repair and maintenance shops in the mineral-oil industry. For the remaining workplaces, the applicable TRK value is 3.2 µg/m3, which, while it reduces the health risk at the workplace, does not completely eliminate it.

Also the EU council has passed directives designed to limit benzene concentration in the air.

EU Directive 98/70/EG of 13 October prescribes as of 1 January 2000 a permissible maximum content of 1% by volume of benzene for all fuels. As of 2005, the content of aromatic hydrocarbons in Otto fuel will be limited to not more than 35 % by volume. 

Directive 1999/C53/07 was submitted on 20 January 1999. It specifies limit values for the protection of health and provides for the uniform recording of said limit values. The upper limit value amounts to 5 µg/m3 and must be reached by the member states in defined steps by 2004.
The directive must be converted into national law by 31 December 2001. For non-compliance with the limit values ”effective, adequate and deterring” sanctions shall be specified.

Moreover, also the quantitatively comparatively small  sources of benzene exposure are to be minimised. Recording them will certainly be simplified when the directives take effect and the total concentrations decrease.