ENTRY 7
The following substances which occur in nature, if they are not chemically modified: Minerals, ores, ore concentrates, raw and processed natural gas, crude oil, coal.
This exemption includes only the above listed groups of substances provided that they occur in nature as defined in Article 3(39), if they are not chemically modified as defined in Article 3(40), irrespective of whether or not they are classified as dangerous according to Directive 67/548/EEC or hazardous according to Regulation (EC) No 1272/2008.
The specific substances covered by the exemption are:
Minerals
Minerals are substances. They may be mono- or multi-constituent or in some cases UVCB substances. A mineral is defined as a combination of inorganic constituents as found in the earth's crust, with a characteristic set of chemical compositions, crystalline forms (from highly crystalline to amorphous) and physical properties. In general minerals are inorganic and most of them are crystalline. In a first step it needs to be assessed whether the mineral has been mined/manufactured in accordance with any method mentioned in the definition of ‘substances which occur in nature’. If it is the case, it needs to be assessed in a second step whether the minerals have not been chemically modified during or after mining/manufacturing according to Article 3(40).
Minerals which occur in nature are covered by the exemption if they are not chemically modified. This applies to naturally occurring minerals, which have undergone a chemical process or treatment, or a physical mineralogical transformation, for instance to remove impurities, provided that none of the constituents of the final isolated substance has been chemically modified. Thus, if both the above conditions are fulfilled, then the mineral is exempted from the obligation to register.
An example of minerals is asbestos. Asbestos is the common name of a number of naturally occurring, hydrated silicate minerals like: Crocidolite (CAS: 12001-28-4); Amosite (CAS: 12172-73-5); Anthophyllite (CAS: 77536-67-5); Actinolite (CAS: 7536-66-
4); Tremolite (CAS: 77536-68-6) & Chrysotile (CAS: 12001-29-5 and 132207-32-0).
Asbestos is exempted from registration provisions, because these minerals occur in nature and are not further chemically modified. However, they are not exempted from other obligations of REACH. Furthermore, asbestos fibres are listed in Annex XVII of REACH ‘restrictions on the manufacture, placing on the market and use of certain dangerous substances preparations and articles’.
Note: Chrysotile is not entirely restricted as it is exempted from the Annex XVII entry for the placing on the market and use of diaphragms containing chrysotile (point (f)) for existing electrolysis installations until they reach the end of their service life, or until suitable asbestos-free substitutes become available, whichever is the sooner.
Other examples of minerals include (but are not limited to):
Dolomite (CAS number 16389-88-1) CaCO3 . MgCO3, a rock-forming mineral;
Limestone (CAS number 1317-65-3), which consists principally of calcium carbonate and may also contain magnesium carbonate;
Barite (CAS number 13462-86-7), which principally consists of barium sulfate; Fluorapatite (CAS number 1306-05-4), the most common phosphate rock mineral.
Note: The exemption does not apply to synthetic substances having the same structures as the natural occurring minerals.
Ores
Ores is a general expression for mineral aggregates or rocks from which metals or metal components can be extracted as well as for mineral aggregates whose mining have an economical benefit.
The ores themselves can be regarded as substances which occur in nature and which therefore are exempted from the obligation to register. It should be noted however, that when ores are extracted with methods not mentioned in the definition of ‘substances which occur in nature’, or with methods which modify the chemical structure of the final substance, the final ‘product’ of the treatment can normally not be regarded as a substance which occurs in nature and hence will need to be registered. However, ores are exempted when processed only by means mentioned in Article 3(39) subsequently undergo a chemical process or treatment, or a physical mineralogical transformation, for instance to remove impurities, provided that none of the constituents of the final isolated substance has been chemically modified.
Example:
The iron ore type ‘banded ironstone formation (BFI)’ which is composed predominantly of magnetite (Fe2+Fe 3+O ) and quartz is processed mechanically in the first steps by 2 4 means of coarse crushing and screening, followed by rough crushing and fine grinding to comminute the ore to the point where the crystallised magnetite and quartz are fine enough that the quartz is left behind when the resultant powder is passed under a magnetic separator. Up to this stage all substances, including the original ore, created through the whole process are regarded as substances which occur in nature.
To convert magnetite to metallic iron it must be smelted or sent through a direct reduction process. Magnetite (or any other iron ore) must be powdered and mixed with coke. During the process in the blast furnace various reduction or oxidation-reactions take place that result in the production of metallic iron, oxides of carbon and other materials collectively known as 'slag:
Air blast and coke: 2C + O2 → 2CO
Carbon monoxide (CO) is the principal reduction agent Stage One: 3Fe2O3 + CO → 2Fe3O4 + CO2
Stage Two: Fe3O4 + CO → 3FeO + CO2 Stage Three: FeO + CO → Fe + CO2
During this manufacturing process different treatments take place which disqualify the final iron as a substance occurring in nature that is not chemically modified:
Heating was not solely applied for removing water
The iron oxide is subject to a reduction/oxidation reaction which is a chemical reaction leading to a new/different substance from the starting material
As a consequence, iron is regarded as a substance for which the registration obligations need to be fulfilled. If analogous processes take place for other metals then also for those metals registration obligations will need to be fulfilled.
Ore concentrates
Ore concentrates are extracted from the original ore mostly by mechanical measures or flotation resulting in mineral-rich fraction which is used for further processing of e.g. metals. Such processes include, but may not be limited to, sorting; magnetic separation; electrostatic separation; preferential crushing, grinding and milling; sieving and screening; hydrocycloning; filtration and flotation.
Therefore ore concentrates are generally regarded as substances which occur in nature provided the manufacturing processes are only mechanical and/or by flotation (e.g. grinding, sieving, centrifugation, etc.). Such naturally occurring ore concentrates are exempted from the obligation to register if they are not chemically modified. Thus, for example, naturally occurring ore concentrates, which have undergone a chemical process or treatment, or a physical mineralogical transformation, for instance to remove impurities, provided that none of the constituents of the final isolated substance has been chemically modified, are exempted.
Raw and processed natural gas
Natural gas is a gaseous fossil fuel which consists predominantly of saturated hydrocarbons. Natural gas can have different compositions depending on the source and can be divided into following groups:
- natural gas from pure natural gas deposits is composed of methane and small amounts of ethane;
- natural gas from coal deposits is composed of methane, small amounts of ethane and variable amounts of nitrogen and carbon dioxide;
- natural gas from crude oil deposits generally contains in addition larger amounts of ethane, propane, isobutane, hexane, heptane, carbon dioxide, hydrosulfides, helium, nitrogen and arsenic compounds;
- natural gas from condensate and distillate deposits which contains besides methane and ethane also higher amounts of hydrocarbons with more than 7 C-atoms.
- However, raw natural gas has to be processed to make it suitable for the use by residential, commercial and industrial consumers. The processed natural gas is almost pure methane and is very much different from the raw natural gas.
The EINECS lists one entry for natural gas which gives the following description: EINECS number: 232-343-9, CAS number: 8006-14-2
Natural gas
Raw natural gas, as found in nature, or gaseous combination of hydrocarbons having carbon numbers predominantly in the range of C1 through C4 separated from raw natural gas by the removal of natural gas condensate, natural gas liquid, and gas condensate/natural gas.
The raw natural gas itself, without further processing, can normally be regarded as a substance which occurs in nature. In addition, the processed natural gas is only exempted under this entry if it does not undergo any chemical modification and thereby satisfies the criteria for Article 3(40).
Note: It has to be emphasised that only methane which is processed from raw natural gas can be regarded as natural gas. Methane processed from other sources than fossil, is not regarded as natural gas.
Crude oil
Crude oil is constituted of complex lipophilic hydrocarbon structures, which is incorporated into the earth’s crust. Crude oil can consist of more than 17,000 constituents and is one of the most complex mixtures of organic compounds. The formation of crude oil is based on sapropel of flat inshore waters emanated from carbohydrates, proteins and fats from small animals and small plants under the influence of bacteria, enzymes, pressure, mineral catalyst etc. The crude oil production is based on mechanical means which qualifies crude oil as a substance which occurs in nature.
However, when processing and separating crude oil, the constituents or mixtures of constituents arising from these processes can normally no longer be regarded as substances which occur in nature which are not chemically modified. EINECS contains many of such substances obtained from crude oil, for example:
EINECS number: 272-871-7, CAS number: 68918-99-0
Gases (petroleum), crude oil fractionation off
A complex combination of hydrocarbons produced by the fractionation of crude oil. It consists of saturated aliphatic hydrocarbons having carbon numbers predominantly in the range of C1 through C5.
For example: Diesel, in general a fuel used in diesel engines, is a specific fractional distillate of petroleum fuel oil, derived from petroleum. Diesel is obtained by chemical modification of petroleum and therefore not exempt from registration.
The EINECS lists diesel fuels which give the following descriptions: EINECS number: 269-822-7, CAS number: 68334-30-5
Fuels, diesel
A complex combination of hydrocarbons produced by the distillation of crude oil. It consists of hydrocarbons having carbon numbers predominantly in the range of C9 through C20 and boiling in the range of approximately 163°C to 357°C (325°F to 675°F).
EINECS Number: 270-676-1, CAS number: 68476-34-6
Fuels, diesel, no. -2
A distillate oil having a minimum viscosity of 32.6 SUS at 37.7°C (100°F) to a maximum of 40.1 SUS at 37.7°C (100°F).
Coal
Coal is a solid fossil fuel formed by carbonisation of plants. There are two types of coal: brown coal and black coal which differ in their carbon content. Brown coal contains 60 – 80 % carbon and black coal contains 80 – 98 % carbon. Coal is usually processed only by mechanical means which qualifies coal as a substance which occurs in nature and may benefit from the exemption if it is not chemically modified.
Charcoal obtained by thermal decomposition of wood is not regarded as a substance which occurs in nature and therefore it is not covered by this exemption.
Entries 7 and 8 cover naturally occurring substances, if they are not chemically modified. Therefore the definitions ‘substances which occur in nature’ and ‘not chemically modified substance’ are here first explained and concern both of the exemptions.
This group of substances is characterised via the definitions given in Articles 3(39) and 3(40):
According to Article 3(39), ‘substances which occur in nature’ means ‘a naturally occurring substance as such, unprocessed or processed only by manual, mechanical or gravitational means, by dissolution in water, by flotation, by extraction with water, by steam distillation or by heating solely to remove water, or which is extracted from air by any means’.
It should be noted as background explanation that prior to REACH naturally occurring substances shared a single EINECS entry which is wider than the current interpretation under REACH:
EINECS No: 310-127-6, CAS No: 999999-99-4
Naturally occurring substances
Living or dead material occurring in nature as such which is chemically unprocessed, or which is extracted from air by any means or physically processed only by manual, mechanical or gravitational means, by dissolution in water, by flotation or by heating solely to remove water.
The REACH definition can be split into several parts in order to obtain a clear understanding:
Naturally occurring substances as such: means, substances obtained, for example, from plants, micro-organisms, animals, or certain inorganic matter such as minerals, ores and ore concentrates, or organic matter such as crude oil, coal, natural gas. It should be noted that whole living or unprocessed dead organisms (e.g. yeast (see Attachment 2), freeze-dried bacteria) or parts thereof (e.g. body parts, blood, branches, leaves, flowers etc.) are not considered as substances, preparations or articles in the sense of REACH and are therefore outside of the scope of REACH. The latter would also be the case if these have undergone digestion or decomposition resulting in waste as defined in Directive 2008/98/EC, even if, under certain circumstances, these might be seen as non-waste recovered materials6.
Naturally occurring substances unprocessed: no treatment at all of the substance takes place.
- Processed only by manual, mechanical or gravitational means: parts of the substance as such may for instance be removed by hand or by machine (e.g. by centrifugation). If minerals are processed only by mechanical methods, e.g. by grinding, sieving, centrifugation, flotation, etc., they are still considered to be the same naturally occurring minerals as originally mined.7
- By dissolution in water: the only solvent which can be used is water. The dissolution by any other solvent or mixture of solvents or mixture of water with other solvents disqualifies the substance as naturally occurring.
- By flotation: physical separation process taking place in water or in a liquid such as oil without chemical reaction.
- By extraction with water: separation process which is based on the different distribution of a certain constituent or constituents from a material by using water with or without conditioners (flocculants, emulsifiers, etc) that only exploit differences in physical behaviour of the constituents in water without chemical reaction.
- By steam distillation: distillation of naturally occurring substances with water vapour as carrier for the separation of certain constituent(s) without chemical reaction.
- Heating solely to remove water: purification or concentration of a substance by removing water by heat while no chemical reaction occurs.
6 This explanation is without prejudice to discussions and decisions to be taken under Community waste legislation on the status, nature, characteristics and potential definition of such materials, and may need to be updated in the future.
7(ECHA, 2012) Guidance for identification and naming of substances under REACH and CLP (ver. 1.2), pages 33-34.
Extracted from air by any means: substances which occur naturally in air, extracted by applying any methods and solvents as far as no chemical reaction occurs.
According to Article 3(40), a ‘not chemically modified substance’ means ‘a substance whose chemical structure remains unchanged, even if it has undergone a chemical process or treatment, or a physical mineralogical transformation, for instance to remove impurities’.
The exemption under point 7 and 8 requires that the substances are substances which occur in nature, if they are not chemically modified. This requirement implies that in order to decide if the exemption applies to a particular substance, both the criteria of:
‘a substance that occurs in nature’ according to the definition in Article 3(39) and
‘not chemically modified’ according to the definition in Article 3(40) have to be fulfilled.
Therefore, in order to benefit from the exemptions under points 7 and 8, a substance must be naturally occurring, which means only processed in accordance with a process listed in Article 3(39). In addition, it must not have undergone a chemical modification as defined by Article 3(40).
This means that, in a first step it needs to be assessed whether the substance in question (e.g. menthol) has been extracted solely with a process listed in Article 3(39). If this is the case, it needs to be assessed in a second step whether the substance has been chemically modified during or after extraction according to Article 3(40)8. It should be noted that processes intended solely to remove impurities are not considered to be a chemical modification, as long as the chemical structure of the molecule is not modified.
However, where a substance undergoes a chemical modification of one or more of the constituents originally present in the naturally occurring substance, hence resulting in a change of chemical structure, a substance would no more be covered by the exemption because it does not conform with the conditions in Article 3(40), even if it was extracted only by the means listed in Article 3(39).
Note that the exemptions in points 7 and 8 do not apply to synthetic versions of the substances described in the relevant sections as such substances do not meet the definition of substances which occur in nature and hence these synthetic versions would
8 Please note that some of the processes mentioned under Article 3(39) may change the chemical structure and thus result in a chemical modification: e.g. simple heating may result in isomerisation which is a chemical modification making the combination of both, the condition of a ‘substance which occurs in nature’ as mentioned under Article 3(39) and the condition ‘not chemically modified’ as mentioned in Article 3(40) meaningful.
be subject to registration if they meet the necessary requirements (see example 4 below).
The following examples illustrate circumstances under which a substance does or does not meet the requirement of substances which occur in nature, if they are not chemically modified.
Example 1:
A substance is obtained in accordance with a steam distillation process of the leaves from Mentha arvensis. The chemical analysis of the Mentha arvensis extract thus manufactured indicates that this substance consists of several stereo-isomers including the constituent (-)-menthol (i.e. (1R,2S,5R)-5-methyl-2-(propan-2-yl)cyclohexanol). All the constituents in the substance were originally present in the leaves. This substance fulfils the requirements for substances which occur in nature, if they are not chemically modified.
Example 2:
The substance isolated in example 1 is further processed by crystallisation9 in water and ethanol to isolate (-)-menthol and to remove other constituents. Although this process did not result in the chemical modification of the substance within the meaning of Article 3(40), the substance does nevertheless not fulfil the requirements for substances which occur in nature, if they are not chemically modified. Therefore the substance does not fulfil the requirements for substances which occur in nature, if they are not chemically modified.
Example 3:
The substance isolated in example 1 is heated solely to remove water. Upon heating the substance isolated in example 1 under vacuum it is converted into a mixture of different constituents including (-)-menthol. Although the isolated substance fulfils the definition of a substance which occurs in nature, it has been chemically modified and therefore does not fulfil the requirements for substances which occur in nature, if they are not chemically modified.
Example 4:
A multi-step synthesis is used for the manufacturing of (-)-menthol. Although this substance consists of the same constituent as the one found in the leaves of Mentha arvensis, it is not a substance which occurs in nature and does therefore not fulfil the requirements for substances which occur in nature, if they are not chemically modified.
9 Crystallisation is not a chemical modification as the chemical structure remains unchanged. Recrystallisation, when done from any solvent other than water (which is often the case), disqualifies such substances from being a “substance which occurs in nature”.
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