Sewage sludge Ordinance (Abfclarification V)

Unofficial table of contents

Abfclarification V

Date of completion: 15.04.1992

Full quote:

" Sewage Sludge Ordinance of 15 April 1992 (BGBl. 912), as last amended by Article 5 (12) of the Law of 24 February 2012 (BGBl). 212) has been amended "

Status:

Last amended by Art. 5 Abs. 12 G v. 24.2.2012 I 212

For more details, please refer to the menu under Notes
The purpose of this Regulation is to implement Council Directive 86 /278/EEC of 12 June 1986 on the protection of the environment, and in particular of the soil, in the use of sewage sludge in agriculture (OJ L 327, 30.12.1986, p. EC No L 181 p. 6).

Footnote

(+ + + Text evidence from: 1.7.1992 + + +) 
(+ + + Official note from the norm-provider on EC law: 
 Implementation of the 
 EWGRL 278/86 (CELEX Nr: 31986L0278) + + +) 

  

Unofficial table of contents

Input formula

On the basis of § 15 (2) of the Waste Act of 27 August 1986 (BGBl. 1410, 1501), the Federal Minister for the Environment, Nature Conservation and Nuclear Safety, in agreement with the Federal Minister for Food, Agriculture and Forestry, and the Federal Minister for Health, decree on the basis of the third sentence of section 11 (2) (3) of the Federal Republic of Germany's federal government. 3 sentence 4 of this law is prescribed by the Federal Minister for the Environment, Nature Conservation and Nuclear Safety: Unofficial table of contents

§ 1 Scope

(1) This Regulation shall take account of the

1.

It is responsible for the treatment of waste water treatment plants and sewage sludge for application to agricultural or horticultural soils.

2.

To apply sewage sludge to agricultural or horticultural soils or to apply it.

(2) The provisions of the Fertilizer Legislation shall remain unaffected. (3) The bodies concerned shall ensure that the limit values set out in this Regulation are as far below as possible. The soil limit values set out in the Regulation have been laid down for the specific conditions of agricultural sewage sludge utilisation. General cultivation restrictions or restrictions of a different kind cannot be deduced from the achievement or exceeding of the values. Unofficial table of contents

§ 2 Definitions

(1) Waste water treatment plants are plants for the treatment of waste water, irrespective of their size and type of treatment. Small-scale plants are plants with several chambers for the treatment of domestic waste water with a water inflow of less than 8 cubic metres per day. Wastewater collection pits without discharge are not waste water treatment plants within the meaning of the regulation. (2) sewage sludge is the one in the treatment of waste water in waste water treatment plants, including related plants for further wastewater treatment the resulting sludge, whether or not dehydrated or dried or treated in some other form. Raw sludge is sludge, the waste water treatment plants are removed untreated. The drainage of raw sludge does not apply as a treatment of sewage sludge. Sludge produced in small-scale sewage treatment plants shall be considered as sewage sludge for the purposes of this Regulation. Sewage sludge composts and sewage sludge mixtures shall also be considered as sewage sludge within the meaning of this Regulation. Sewage sludge mixtures are mixtures of sewage sludge with other suitable substances according to Annex 2, Tables 11 and 12 of the Fertilizer Ordinance, in the version in force. Sewage sludge composts are composted sewage sludge mixtures. (3) Field feed for the purposes of this Regulation are plant species cultivated on arable land and the vegetative parts of which are intended for feeding animals to animals. The cultivation of maize does not count for the cultivation of forage within the meaning of this Regulation. Unofficial table of contents

§ 3 Conditions for application

(1) sewage sludge may be applied to agricultural or horticultural soils only in such a way that the good of the general public is not impaired and the application by type, quantity and time to the nutrient requirements of the plants is not impaired. Taking into account the nutrients and organic substance available in the soil, as well as the location and cultivation conditions. In addition, the provisions of the fertilizer law apply to the application of sewage sludge. (2) The operator of a waste water treatment plant is obliged to apply sewage sludge for the first time on an agricultural or a non-agricultural basis. (3) The soil studies referred to in paragraph 2 shall be carried out in accordance with the procedure laid down in paragraph 2 of this Annex, and shall be subject to the following conditions: distance of 10 years. The competent authority shall, in consultation with the competent agricultural authority, arrange for soil investigations to be repeated at shorter intervals if, according to the results of the sewage sludge and soil investigations carried out, the following shall be: and taking into account the amount of application and other causes of heavy metal pollution, the values referred to in § 4 (8) shall be exceeded. It may limit the additional soil studies to certain surface units and heavy metals. (4) sewage sludge may only be applied if the soil has a pH value, the content of the plant-available phosphate, potassium and magnesium. has been investigated. The operator of the waste water treatment plant shall bear the costs of carrying out this land inspection. (5) sewage sludge may only be delivered to or applied to soils which are used in agricultural or gardening grounds if: at intervals of not more than six months, samples of the sewage sludge by means of a body designated by the competent authority on the contents of lead, cadmium, chromium, copper, nickel, mercury and zinc, on the sum of the organic halogen compounds as adsorbed organic-bonded halogens (AOX), total and ammonium nitrogen, phosphate, potassium, magnesium, as well as the dry residue, the organic substance, the basic active substances and the ph-value are investigated. The competent authority may extend the investigation to other ingredients. It can shorten the distance between the examinations of the sewage sludge up to two months. In doing so, it may limit the studies to individual heavy metals. (6) For application to agricultural or horticultural soils, sewage sludge may only be dispensed or applied if it is applied for the first time before and after the application. at intervals of not more than two years, samples of the sewage sludge on the contents of the organic-persistent pollutants

-

polychlorinated biphenyls and

-

polychlorinated dibenzodioxins and dibenzofurans

shall be examined. The third sentence of paragraph 5 shall apply accordingly. The investigation shall be carried out by one of the bodies designated by the competent authority. (7) The operators of waste water treatment plants shall have the sampling and testing referred to in paragraphs 2, 3, 5 and 6 following the instructions in the Annex. (8) The provisions of paragraphs 2 to 7 shall not apply in the case of the application of sludge from small-scale agricultural holdings on farm-owned arable land. Sludges from such installations shall be analysed prior to the initial application to the parameters referred to in paragraph 5. The results shall be forwarded without delay by the operator of the plant to the competent authority and the competent agricultural authority. (9) In the case of the application of sewage sludge from waste water treatment plants, to the treatment of After an initial investigation pursuant to paragraph 2 with the consent of the competent authority, the studies may be carried out after an initial investigation pursuant to paragraph 2, with the consent of the competent authority, with the consent of the competent authority. in accordance with paragraphs 3 and 6. The studies referred to in paragraph 5 shall be carried out at intervals of not more than two years; the competent authority may reduce the distance of the examinations up to six months, or extend it up to 48 months, and the investigation into further (10) Investigations referred to in paragraphs 2 to 7 to 31 December 1998 shall apply only to the order of the competent authority in respect of small-scale installations of individual households in the area referred to in Article 3 of the Agreement on the Ification of the Community (11) A position referred to in the first paragraph of paragraph 2, the first sentence of paragraph 5 and the third sentence of paragraph 6 shall be determined if: the applicant has the necessary technical expertise, independence, reliability and equipment. The provision shall be made by the competent authority of the country in which the applicant has its registered office and shall be valid throughout the territory of the Federal Republic of Germany; if there is no registered office in the territory of the country, the country in which the activity is carried out shall be the responsibility of the Member State. Paragraphs 2, 5 and 6 shall be exercised as a priority. The provision may be provided with a reservation of the revocation, a limit, conditions, conditions and the reservation of conditions. The competent authority may require a nationally active applicant to obtain a valid accreditation for compliance with the requirements of DIN EN ISO/IEC 17025:2005 (to be received by Beuth-Verlag GmbH, 10772 Berlin, Germany). Submitted in the form of an archive with the German National Library in Leipzig), which refers to the parameters and the methods of examination referred to in Annex 1. Procedures in accordance with this provision may be carried out via a single entity. The examination of the application for the determination of a body must be completed within three months; § 42a (2) sentences 2 to 4 of the Administrative Procedure Act shall apply. (12) Equivalent recognition from another Member State of the The European Union or any other State Party to the Agreement on the European Economic Area shall be the same as the provisions of the first sentence of paragraph 2, the first sentence of paragraph 5 and the third sentence of paragraph 6. When examining the application for the determination referred to in the first sentence of paragraph 2, the first sentence of paragraph 5 and the third sentence of paragraph 6, the application shall be made from another Member State of the European Union or of another State Party to the Agreement on the European Economic Area National references shall be the same if they show that the applicant fulfils the relevant requirements of the first sentence of paragraph 11 or the requirements of the issuing State, which are essentially comparable in view of their objectives. Proof of recognition within the meaning of the first sentence or any other evidence provided for in the second sentence shall be submitted to the competent authority prior to the commensurate of the activity in the original or in copy. A certification of the copy as well as a certified German translation can be requested. Unofficial table of contents

§ 4 Movement bans and restrictions

(1) The application of raw sludge or sludge from other waste water treatment plants than for the treatment of household waste water, municipal waste water or waste water with similarly low levels of pollution on agricultural or gardening Soils are prohibited. (2) The application of sewage sludge to vegetable and fruit trees is prohibited. Arable land, which is also used for the cultivation of agricultural vegetables, is prohibited in the year of the application of the sewage sludge and the following year in the cultivation of field vegetables. (3) On arable land used for the cultivation of field fodder or for the cultivation of agricultural vegetables. Sugar beet, to the extent that the sugar beet leaf is fed, is used only before sowing, followed by a deep incorporation. In the cultivation of silo and green maize, the sewage sludge is to be incorporated into the soil before sowing. (4) The application of sewage sludge to permanent pasture is prohibited. (5) The application of sewage sludge to soil-based soils is prohibited. (6) Application of sewage sludge on agricultural or horticultural soils in nature conservation areas, national parks, national natural monuments, natural monuments, protected landscape components and legally protected biotopes in the sense of § § § § § 30 of the Federal Nature Protection Act is prohibited, unless it is (7) The application of sewage sludge to soils in zones I and II of water protection areas as well as to soils in the area of the riverside strips up to a width of 10 metres is prohibited. Further regulations for water protection areas according to water regulations shall remain unaffected. (8) The application of sewage sludge to agricultural or horticultural soils is prohibited if the soil investigations in accordance with § 3 Paragraph 2 or 3 shows that the contents of the following heavy metals exceed at least one of the following values (milligrams per kilogram of dry matter):

Lead	100
Cadmium	1.5
Chrome	100
Copper	60
Nickel	50
Mercury	1
Zinc	200

In the case of soils which are classified as light soils in the context of the soil estimation and whose clay content is less than 5 of the hundred or whose investigation has a pH of more than 5 and less than 6 in accordance with Article 3 (4), an application of Sewage sludge shall be prohibited even if the following values (milligrams per kilogram of dry matter) are exceeded in the case of the heavy metals cadmium and zinc:

Cadmium	1
Zinc	150

(9) The application of sewage sludge to agricultural or horticultural soils is prohibited, provided that a target value of pH 5 or less in the context of proper management is sought for these soils, or a pH of 5 or less in the case of such soils. the investigation according to § 3 (4) is established. Soils, whose target value is above pH 5 in the context of proper management, require this value to be underwritten and the costing with fertiliser is required before the sludge is applied to the sewage sludge. The calculation of the quantity of lime shall take account of the basic components to be subsequently applied in the sewage sludge. (10) The application of sewage sludge to agricultural or horticultural soils shall be prohibited if the sludge is removed from the soil in the form of a water. Investigations of sewage sludge in accordance with § 3 (6) show that the contents of the following organic-persistent pollutants exceed at least one of the following values:

-

polychlorinated biphenyls (PCBs), each 0.2 milligrams per kilogram of sludge dry mass for the components number 28, 52, 101, 138, 153, 180;

-

polychlorinated dibenzodioxins/dibenzofurans (PCDD/PCDF) 100 nanograms of TCDD toxicity equivalent (according to the calculation formula in Annex 1) per kilogram of sludge dry matter.

(11) The application of sewage sludge to agricultural or horticultural soils is prohibited if the sludge studies in accordance with section 3 (5) show that the sum of the organohalogen compounds, expressed as sum parameters, is prohibited. AOX, 500 milligrams per kilogram of sludge dry mass. (12) The application of sewage sludge to agricultural or horticultural soils is prohibited if sewage sludge tests in accordance with Section 3 (5) show that the contents of the sludge are after heavy metals, at least one of the following values: (milligrams per kilogram of sludge dry mass):

Lead	900
Cadmium	10
Chrome	900
Copper	800
Nickel	200
Mercury	8
Zinc	2 500

In the case of soils classified as light soils within the framework of the soil estimation and whose clay content is less than 5 of the hundred or whose investigation has resulted in a pH of more than 5 and less than 6 in accordance with Article 3 (4), the following values shall be set out in the first sentence: for cadmium and zinc:

Cadmium	5
Zinc	2 000

(13) In the production of sewage sludge compost and sewage sludge mixtures, the pollutant values referred to in paragraphs 10, 11 and 12 shall be based on the sludge and the aggregates used before mixing and on the produced sewage sludge. Compost or the herposed mixture. In the case of the application of a mixture made using sewage sludge, the quantity of pollutants permitted by the product of paragraphs 10, 11 and 12 and the quantity of application permitted pursuant to Article 6 (1) may be obtained. (14) sewage sludge may only be stored on or in the vicinity of the application area, to the extent that this is necessary for the application. Unofficial table of contents

§ 5 Exceptions

The competent authority may, in agreement with the competent nature conservation authority, authorise in individual cases the application of sewage sludge to arable land in nature reserves, national parks, national natural monuments, natural monuments, protected landscape components and legally protected biotopes within the meaning of § 30 of the German Federal Nature Protection Act (Bundesnaturschutzgesetz). Unofficial table of contents

§ 6 Set-up

(1) For the soils referred to in § 1 above, no more than 5 tonnes of dry mass of sewage sludge per hectare may be applied within three years. Sewage sludge composts may be applied within 3 years up to 10 tonnes of dry mass per hectare if the pollutant contents in the sewage sludge compost are half of the heavy metal contents permitted in accordance with § 4 (12) and half of the permissible levels according to § 4 (2) In the case of the application of a mixture using sewage sludge, the amount of application permitted in accordance with paragraph 1 shall be based on the sewage sludge used and not to the mixture. The proportion of sewage sludge must be demonstrated by the supplier and made known to the user. Irrespective of this, Section 4 (13) sentence 2 applies. Unofficial table of contents

§ 7 Post-compliance

(1) Not later than two weeks before the discharge of the sewage sludge, the operator of the waste water treatment plant or a representative of a third party of the competent authority responsible for the application area and the agricultural authority shall show the intended Application by sending a copy of the completed delivery note in accordance with the specimen in Annex 2 to this Regulation. (2) The operator of the waste water treatment plant shall record the date of the delivery of the sewage sludge on the delivery note and Passes this to the carrier. The delivery note shall be carried in the vehicle during transport. The delivery and the application of the sewage sludge shall be confirmed by the customer. (3) The customer and the carrier shall each retain a copy of the delivery note, a further copy of which shall be sent by the carrier to those for which the delivery note is Waste water treatment plant and the authority responsible for the application area, the original to the operator of the waste water treatment plant. The original shall be kept for 30 years from the date of the levy and shall be submitted to the competent authorities upon request. In the implementation of paragraphs 1 and 2 and of the first sentence, the possibilities of electronic data processing may be used. (4) The obligations under paragraphs 1 to 3 shall apply even where operators of waste water treatment plants are (5) The competent authority for the area of application may, in consultation with the agricultural authority responsible for certain waste water treatment plants, be able to rely on the indications referred to in paragraph 1 (6) When sewage sludge is transferred to the scope of the Waste law shall be subject to the obligations of the operator of the waste water treatment plant in accordance with paragraphs 1 to 4 for the owner of the sewage sludge which spends or spends the sewage sludge in the scope of the waste law. (7) Operator of the waste water treatment plant. Waste water treatment plants shall keep registers containing the following information:

1.

the quantities of sludge produced and the quantities of sludge supplied to agriculture (in tonnes of dry matter),

2.

Properties of sewage sludge in accordance with Article 3 (5),

3.

the nature of the treatment of sewage sludge,

4.

name and address of the consignee of the sludges, impact-specific name of the application area, ordered by parcel number,

5.

Results on the soil investigations carried out, broken down by blows and ordered by parcel number.

Until 31 March of the following year, the operators of waste water treatment plants shall forward these data for the previous calendar year to the competent authorities responsible for the implementation of the Sewage Sludge Regulation. (8) The Authorities responsible for sewage sludge ordinance shall send the information referred to in paragraph 7 (1) to (3) to the competent national competent authorities for the previous calendar year by 31 August of a subsequent year. The countries are conducting the combined data to the Federal Minister for the Environment, Nature Conservation and Nuclear Safety. The Federal Minister for the Environment, Nature Conservation and Nuclear Safety prepares a summary report for the Commission of the European Communities every four years, for the first time in 1991, on the basis of the information provided by the countries. (9) The obligations laid down in paragraphs 1 to 7 shall include the operators of waste water treatment plants for the treatment of domestic waste water, municipal waste water or waste water with a similarly low pollution level and with a smaller Size as 1,000 inhabitants excluded. (10) For the recovery of sewage sludge, for which the The provisions of this Regulation shall not apply, with the exception of Section 2 (1) (2) and Section 23 (2) of the Detection Regulation, to the provisions of the Verification Regulation. Unofficial table of contents

§ 8 Development Plan

Each year, the competent agricultural authorities of the countries or third parties responsible for the agricultural sector shall draw up an application plan on the sewage sludge which has been applied in the course of the calendar year. Unofficial table of contents

§ 9 Administrative Offences

(1) In the sense of § 69 (1) (8) of the German Circular Economy Act, who intentionally or negligently acts in the sense of the law

1.

, contrary to § 3 (4) sentence 1, sewage sludge without the prescribed soil tests,

2.

, contrary to the first sentence of Article 3 (5) or the first sentence of Article 3 (6), sewage sludge, without the prescribed examination, gives or applies to the application,

3.

Contrary to § 3 (8) sentence 2, sewage sludge is not analysed,

4.

, contrary to § 3 (9) sentence 2, sewage sludge, without the prescribed examination for application, gives off or applies,

5.

contrary to § 3 (10) of a fully-enforceable order, does not comply properly or not in good time,

6.

, in accordance with Article 4 (1), (2) sentence 1, (4), (5) or (6), first sentence, first half-sentence, or (7) to (11) sludge,

7.

Contrary to the second sentence of Article 4 (2), including in conjunction with the first sentence of paragraph 3, the plants referred to therein shall also be grown or the soil shall not be subject to substantial processing,

8.

Contrary to § 4 (3) sentence 2, the sewage sludge does not enter the soil before the sowing,

9.

, contrary to Article 4 (12), sewage sludge is applied to agricultural or gardened soils,

10.

, contrary to Article 4 (13), sentence 2, applies to sewage sludge mixtures,

11.

, contrary to Article 4 (14), sewage sludge is stored on or near the surface of the application, or

12.

Contrary to § 6, more than the quantities of dry matter referred to in this section are applied to sewage sludge, sewage sludge compounder or a mixture using sewage sludge.

(2) In the sense of § 69 (2) (15) of the German Circulatory Economic Law, who intentionally or negligently acts in accordance with the law of the law

1.

Contrary to the third sentence of Article 3 (8), the results of the investigation are not, or are not, supplied to the competent authorities

2.

Contrary to Article 7 (1), the application of sewage sludge does not indicate or does not display in time,

3.

Contrary to Article 7 (2), second sentence, the delivery note is not carried out during transport in the vehicle,

4.

does not fill the delivery note in accordance with Annex 2 to this Regulation, either correctly or not completely, or a copy of the delivery note is not retained for 30 years, contrary to § 7 (3) sentence 2, or if requested by the competent authority on request shall be presented for consideration or

5.

, contrary to § 7, paragraph 7, the register does not lead, not properly or incompletely, or does not forward the information in time or not.

Unofficial table of contents

Section 10 Entry into force, expiry of the external force

This Regulation shall enter into force on the first day of the third calendar month following the date of delivery. Unofficial table of contents

Final formula

The Federal Council has agreed. Unofficial table of contents

Annex 1 sampling, sample preparation and investigation of sewage sludge and soil

(Fundstelle des Originaltextes: BGBl. I 1992, 917-930)

1

Sewage sludge

1.1

Sampling

For the examinations of the sewage sludge prescribed in accordance with § 3, the sampling according to DIN 38414, part 1 (November 1986 edition) * 1) takes place in the state of the sewage sludge, as this is applied to the agricultural areas.
To ensure representative analytical results, collection samples shall be prepared in the following manner:
Before the date of the investigation, five litres of sludge must be removed from at least five different sewage sludge levies, and the sludge is to be collected in a suitable container (e.g. aluminium) for the collection sample. The sampling should, if possible, be several days apart.
A partial quantity is taken from the carefully mixed sample, which is sufficient to ensure four parallel investigations for all the prescribed test parameters.
The partial quantity is filled into a well-sealable, suitable container (for example made of aluminum) and delivered immediately to the examination site.

1.2

Sample Preparation

The sludge sample which is to be examined is mixed continuously immediately prior to the removal of a sample. If there is a risk of separation, the sub-sample is to be taken during mixing.
For all the examination parameters determined from the dry mass, a partial sample shall be taken, which shall be at least sufficient to ensure four parallel investigations.
A partial sample shall also be taken for freeze-drying, which shall be at least sufficient to carry out four parallel provisions in accordance with points 1.3.3.1 and 1.3.3.2.
The freeze-drying must be carried out in such a way that evaporation losses of the substances to be investigated are avoided. In particular, care must be taken to ensure that the sample does not baptize during freeze-drying. Sewage sludges with a high water content should be partially dewatered by centrifugation before freeze-drying. The separated centrifugate should not contain any particles.

1.3

Conduct of investigations

When working with fresh and freeze-dried sewage sludge, the usual safety rules for working in microbiological laboratories * 2) must be observed. If the results of the examination are not affected, a subset of the fresh or freeze-dried sludge for the appropriate examinations (e.g. by heating the sample for 30 minutes at 70 degrees C).
At least two parallel investigations shall be carried out for each examination parameter, and the arithmetic mean of the two values shall be indicated as a result. Equivalent methods are permitted.

1.3.1

Determination of heavy metals, nutrients, pH, dry residue, loss of ignition and adsorbed organically bound halogens (AOX)

The prescribed studies of these parameters shall be carried out in accordance with the methods of investigation listed in Table 1.

1.3.2

Determination of the basically active substances

I.

Purpose and scope

The method is applicable to sewage sludges which contain calcium and magnesium in a basic effective form (e.g. as oxide, hydroxide and carbonate).

II.

Principle

The substance is brought into solution with acid and the acid excess is titrated back. The basic substances are given as% CaO.
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* 1) Reference source see section 5.
* 2) See e.g. Laboratory safety. Preliminary recommendations for the handling of pathogenic microorganisms and for the classification of microorganisms and pathogens in accordance with the dangers arising in dealing with them in: Bundesgesundheitsblatt 24 Nr. 22 vom 30. October 1981, 347-359
-----

III.

Chemicals

III.1

Hydrochloric acid solution

c (HCL) = 0.5 mol/l

III.2

Sodium hydroxide solution

c (NaOH) = 0.25 mol/l

III.3

Phenolphthalein solution

w (phenolphthalein) = 1% in ethanol (w = 96%)

IV.

Usual laboratory equipment

V.

Implementation * 3)

V.1

Sample preparation

The sample is dried and homogenized according to DIN 38 414 Part 2 * 1) at 105 ° C and homogenized in accordance with DIN 38 414 Part 7 * 1). The sample is carefully weighed to 1 mg on an analysis scale, transferred to a 200 ml graduated flask and 100 ml hydrochloric acid. in accordance with Section III.1. The measuring piston is left standing in the cold until the end of the main reaction. The mixture is carefully heated and kept at the boil for five minutes, so that no losses of hydrochloric acid occur. After the end of the solvent, the mixture is cooled down, filled up to the mark with water, shaken and filtered.

V.2

Method from FOERSTER

50 ml (A) of the hydrochloric acid filtrate (according to section V.1) are pipetted into a 200 ml graduated flask and titrated with sodium hydroxide solution according to section III.2 with the addition of phenolphthalein solution according to section III.3. The still weakly acidic liquid is boiled up in order to remove the carbon dioxide and the titration is continued until a turbidity occurs (spent amounts of lye = X ml).
The mixture is then cooled, filled up with water to the mark, shaken and filtered. In 100 ml of filtrate = 0.25 g of substance, the titration is brought to an end (spent amount of lye = y ml).

VI.

Calculation

The content of basic substances W (deep) bas in% CaO is calculated according to the following formula:

		X
W (deep) bas =	(A-0,5 B) X C = (50-	-	-y) X 1,402
		2
B = (x + 2 y) (ml)
-A:	Submission of hydrochloric acid solution in ml (factor 1.00)
-B:	Consumption of sodium hydroxide solution in ml (factor 1.00)
-x:	Consumption of sodium hydroxide solution up to the occurrence of turbidity
-y:	Consumption of sodium hydroxide solution-Measurement solution after filtration
-C:	Conversion factors
C (deep) 1	= 1,402 for CaO
C (deep) 2	= 2,502 for CaCO (deep) 3

1.3.3

Determination of polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDFs)

1.3.3.1

Determination of polychlorinated biphenyls

I.

Principles

The following investigation procedure is suitable for the determination of the six selected PCB congeners in the sewage sludge, which is prescribed for preventive reasons according to § 3 (6).
It is based on the standards DIN 51 527 part 1 (4) * 1), DIN 38 407 part 2 (DEV F2, draft 1985) * 1) (5) and ISO/TC 190 /SC 3 N2 Rev. 3 (18), as well as on the results of the ring trials carried out by the working party 2 of the Concerted Action COST 681 in the The European Community was implemented (6, 7). In addition, the more recent literature has been included (8, 9, 10, 11, 13, 14, 15, 19).
The procedure describes tried-and-tested procedures which can only be applied by or under the supervision of analysts who have experience in trace analysis with gas chromatography and for the necessary measures to be taken in order to: Ensure quality assurance and control (see Section IX).
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* 3) See Method Book Bd. II of the VDLUFA "Investigation of fertilizers".
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Only if the gas-chromatographic separation of the PCB congeners by interfering co-eluting substances is disturbed in such a way that a safe identification/quantification is not possible, can only deviate from the predetermined working steps. In these exceptional cases, it may be useful to repeat predetermined cleaning steps or to carry out additional other cleaning methods. Furthermore, it may be necessary here to use a mass spectrometric detector.
In order to separate the PCBs from some chlorinated hydrocarbons, such as, for example, p, p-DDT, dieldrin, heptachloric epoxide, HCH isomers and others, a silica gel separation column can be used as an additional purification step (see e.g. 15, 18, 19 and 21).
Since the procedure described here is based on the limit values of the Abfclarification V, in the determination of very low PCB contents, both the aliquoting and dilution volumes as well as the added masses have to be changed at internal standard. .

II.

Descriptive Summary

After the addition of internal standard, the freeze-dried sewage sludge sample is extracted with n-hexane in the soxhlet. PCB congeners optionally contained in the extract are largely freed from interfering accompanying substances by purification steps, separated by capillary gas chromatography and determined using an electron capture detector (ECD) (see diagram in Figure 1). 1).

III.

Chemicals

All chemicals must have a degree of purity which allows the determination of the PCB components within the limits of the detection limit of the process. This is to be checked by means of regular blind-value studies and, if necessary, to be ensured by additional cleaning measures.

III.1

Solvent for residue analysis

n-dodecane, n-hexane and isopropanol, if necessary, purified further, for example by distillation via a highly effective distillation column.

III.2

Water, demineralized

III.3

Drying agent

III.3.1

Sodium sulphate, anhydrous

The sodium sulfate, if necessary, is annealed in a muffle furnace for at least two hours for purification and drying at 550 degrees C.

III.3.2

magnesium perchlorate

III.4

Tetrabutylammonium hydrogen sulphate (TBA)

III.5

Sodium sulphite

III.6

TBA-sulphite reagent

Example 3 3.39 g of tetrabutylammonium hydrogen sulfate are exactly weighed into a 100 ml graduated flask to 0.01 g, dissolved in demineralized water and filled with water. The solution is extracted three times with 20 ml of n-hexane in a 250 ml separating funnel and saturated with 25 g of sodium sulfite. The solution should not be kept for more than one month.

III.7

Silver nitrate

III.8

Packing materials for column chromatography

III.8.1

Aluminium oxide

Aluminum oxide W 200, basic or neutral, activity Super 1 Woelm or equivalent, is dried for 16 hours at 150 degrees C or for two hours at 400 degrees C.
89 g of the dried aluminium oxide are mixed with 11 g of water and shaken in a sealed bottle until all lumps have disappeared. The mixture is stored in a sealed bottle for at least 16 hours prior to the first use.

III.8.2

Silica gel

Silica gel 60, 0,063-0, 200 mm (70-230 mesh), e.g. Merck Quality No. 7754, or equivalent, is dried for 16 hours at 200 degrees C, cooled in the desiccator over magnesium perchlorate and stored there for a maximum of 14 days.

III.8.3

Silver nitrate/silica gel mixture

10 g of silver nitrate are dissolved in 40 ml of water and the mixture is added in portions in 90 g of activated silica gel according to section III.8.2. The mixture is shaken until clumps are no longer present and then heated to 120 ° C. in a drying cabinet within five hours from 70 ° C. The mixture is then heated to 120 ° C. in a drying oven for 5 hours.
For activation, the mixture is heated to 125 ° C. for 15 hours, cooled in the desiccator via magnesium perchlorate, filled into a brown bottle, and stored there for a maximum of 14 days.

III.9

Gases

III.9.1

Carrier gas

Helium or hydrogen, each with a volume fraction of >-99.99%.

III.9.2

Auxiliary gases

Gas mixture consisting of 95 parts by volume of argon and five parts by volume of methane; alternatively nitrogen, each with a volume fraction of > 99.99%. Nitrogen, purified and oil-free for the concentration of small extract volumes.

III.10

Calibrating and reference substances

III.10.1

Single PCB Components

2,4,4 '-trichlorobiphenyl	PCB 28
2,2 ', 5,5'-tetrachlorobiphenyl	PCB 52
2,2 ', 4,5,5'-pentachlorobiphenyl	PCB 101
2,2 ', 3,4,5,5'-hexachlorobiphenyl	PCB 138
2,2 ', 4,4', 5,5 '-hexachlorobiphenyl	PCB 153
2,2 ', 3,4,4', 5,5 '-heptachlorobiphenyl	PCB 180
Decachlorobiphenyl	PCB 209 (Internal Standard)

As stock solutions, the individual components are dissolved as a mixture with a content per component of, for example, 10 myg/ml in hexane. The working standards are prepared by diluting the stock solution (s) with n-hexane in such a way that, under the given gas-chromatographic conditions, a linear display of the electron capture detector over the selected working area is obtained. In general, contents of 2 Myg/l to 20 Myg/l are sufficient for this purpose.
To all working standards, an equally large mass of decachlorobiphenyl is added as an internal standard. This mass should be dimensioned in such a way that the measuring signal of the internal standard in the linear operating range is greater than the measurement signal of the individual PCB components of the working standard with the highest PCB content. In the case of a working range of 2 Myg/l to 20 Myg/l and an injection volume of 1-2 Myl, for example, a concentration of an internal standard of 20 Myg/l could be sufficient.
The sewage sludge sample is also treated with such a much internal standard prior to extraction that the measurement signal of the internal standard in the measuring solution according to V.2.1.2 or V.2.2 is greater than the measurement signal of the individual PCB components in the measuring solution. of this solution, but not more than ten times its value. An addition of 500 ng of decachlorobiphenyl gives, in the procedure described here, a corresponding content in the measuring solution of 20 Myg/l.

III.10.2

Technical PCB mixtures

Technical PCB mixtures are used for the recognition of the peak pattern and for the assessment of the separation performance of the gas chromatographic system. In addition to the individual products chlorphene (high) R A30, A40, A50 and A60 or the corresponding Arochlormixtures (high) R, for the above-mentioned purpose, a mixture of chloropes (high) R A40 and A60, for example with a concentration of 2 in each case, is particularly suitable for the above-mentioned purposes. Myg/ml used.

IV.

Devices

All equipment which comes into contact with the sample and its solutions/extracts must have a degree of purity which permits the determination of the PCB components within the limits of the detection limit of the method. This is to be checked by means of regular blind-value studies and, if necessary, to be ensured by additional cleaning measures.

IV.1

Usual laboratory equipment

IV.2

Freeze-drying plant

IV.3

Capillary gas chromatograph with electron capture detector (ECD)

IV.4

Gas-chromatographic separation column

See DIN 51 527 part 1* 1), section 5.3 (4) and DEV F2 * 1), section 7.2.2 (5).

IV.5

Columns for liquid chromatographic pre-purification

Glass columns of different lengths (e.g. 150 to 250 mm) with an inside diameter of 6 mm below to a tip with approx. 40 mm in length and provided with a reservoir at the top end, e.g. 50 mm length with 20 mm i.D.
In the case of the separating columns described below, the elution behavior of the PCBs on the column is to be checked regularly with a mixture of the six PCB components and decachlorobiphenyl, but at least for each new batch of the packing material.

IV.5.1

Aluminium oxide separation column

A chromatography column according to section IV.5 is provided with a glass wool plug and is filled with 2 g of aluminum oxide slurred in n-hexane (see section III.8.1).

IV.5.2

Silver nitrate/silica gel separation column

A glass column according to section IV.5 is provided with a glass wool plug, with a 5 mm high layer of anhydrous sodium sulphate, above it with 2 g of silver nitrate/silica gel mixture according to section III.8.3 and above again with a 5 mm high Layer of anhydrous sodium sulfate filled. The column must be freshly prepared before each cleaning.

V.

Sample preparation

V.1

Extraction

2 grams of the freeze-dried and in accordance with DIN 38 414 Part 7 (3) * 1) in an analysis mill comminuted and homogenized sewage sludge are weighed into an extraction sleeve (pre-purified if necessary) to 1 mg exactly, with 500 ng of decachlorobiphenyl as internal standard (see section III.10.1) and extracted in the Soxhlet extractor with n-hexane (e.g. 70 ml). The duration of the extraction is calculated in such a way that about 80-100 extraction cycles are carried out. If necessary, the extract is filtered, by gentle distillation, if necessary after addition of a little n-dodecane (e.g. 100 Myl of a solution of 20 Myg/Myl n-dodecane in n-hexane) to about 5 ml, concentrated quantitatively into a 10 ml graduated flask. over-led and filled with n-hexane.

V.2

Cleaning of the extract

In order to separate the PCBs from interfering accompanying substances, two equivalent procedures are described here (see diagram in FIG. 1).

a)

A two-stage procedure comprising the removal of sulfur and sulfur-containing compounds with TBA and column chromatography with alumina.

b)

A single-stage cleaning with a silver nitrate/silica gel separation column.

As a rule, both procedures are sufficient in the case of samples with little load.

V.2.1

Cleaning with TBA and aluminium oxide

V.2.1.1

Removal of sulphur and sulphur compounds (22)

2 ml of the extract according to section V.1 or, if appropriate, another suitable asliquot are mixed with 1 ml of isopropanol and 1 ml of TBA-sulphite reagent and shaken vigorously for at least two minutes. If a crystalline precipitate is not formed after this, 100 mg of sodium sulfite are thus often added and shaken until a crystalline precipitate remains. After the addition of 5 ml of water, the mixture is shaken again for two minutes. The hexane phase is separated off and the aqueous phase is subsequently extracted twice with a little n-hexane. The combined organic phases are dried with sodium sulfate and filtered off. The sodium sulfate is washed twice with a little n-hexane, and the entire n-hexane phase is gently concentrated to 1 ml with nitrogen.

V.2.1.2

Aluminium oxide separation column

The n-hexane phase constricted to 1 ml, in accordance with V.2.1.1, is applied quantitatively by means of a pipette to the aluminium oxide separation column, which has been pre-washed with n-hexane, in accordance with section IV.5.1. The residue vessel is washed with 0.5 ml of n-hexane. The hexane is placed on the surface of the pack by means of the pipette when the meniscus of the solution is just seeping. This rinsing process is repeated twice. The column is then added in portions with 5 ml of n-hexane or, respectively, as described above. of a volume determined in accordance with Section IV.5. The eluate is concentrated in a gentle stream at room temperature in a stream of nitrogen to about 3 ml, and the mixture is made up to 5 ml with n-hexane for GC analysis in the measuring flask.

V.2.2

Cleaning with silver nitrate/silica gel

2 ml of the extract according to section V.1 or, if appropriate, another suitable aliquot shall be applied to the silver nitrate/silica gel pre-washed with n-hexane in accordance with section IV.5.2.
If the meniscus of the extract is seeping straight into the surface of the pack, 40 ml of n-hexane or another sufficient volume to completely elution the PCBs are placed on the column in portions. The entire eluate is gently concentrated to about 3 ml and made up to 5 ml with n-hexane for GC analysis in the measuring flask.

VI.

Gas chromatographic determination

The identification and quantification of the six PCB congeners in the purified extract is carried out using capillary gas chromatography and electron capture detector. The separation performance of the GC system must be optimized in such a way that a sufficient resolution of the components PCB 28 and PCB 31 is achieved. For the optimization of GC working conditions, see DIN 51 527 part 1* 1), sections 9.3 and 10 (4), DEV F2 * 1), sections 7 and 10.4 (5), Beck and Mathar (8) as well as VDLUFA (10).
It is recommended that the identification of the PCB components with two capillary separation columns of different polarity be secured. Furthermore, it must be ensured that no interference occurs between the PCB components 101 and o, p '-DDE or alpha-endosulfan as well as between PCB 138 and p, p' -DDT.
In addition to PCBs, the sewage sludge sample also contains tetrachlorodiphenylmethanes (such as Ugilec 141), a large proportion of the corresponding isomers are likewise present in the eluate of the separation column (n) and can interfere with the identification or the quantification of the PCB component 153. In this case, a mass spectrometry detector should therefore be used for the perfect quantification of this component (see, for example, 11, 15, 16, 17, 19).

VII.

Calibration

The gas-chromatographic separation system is calibrated in the linear measurement range of the ECD. In this case, multi-component solutions are expediently used as working standards (see section III.10.1).
The linear calibration functions of the individual PCB components are determined on the basis of DIN 38 402 part 51 * 1) (1) by at least five calibration concentrations distributed equidistantly across the working area as follows:
The working standards doped with internal standard are injected in ascending concentrations in the gas chromatographs under the same conditions as in the sample measurement. The measured values Y (deep) iej obtained are set in relation to the measured values of the internal standard Y (deep) lej. Likewise, the mass concentrations beta (deep) iej and beta (deep) lej on which the measured values are based are also based on the measured values. The calibration functions (1) are calculated from these ratios by linear regressions:

Y (deep) ie beta (deep) ie 
 --------- = m (deep) il x ------------ + b (deep) il (1) 
 Y (deep) le beta (deep) le   

This means:

Y (deep) ie

Measured value of PCB i during calibration; depending on beta (deep) ie; unit evaluation-dependent; e.g. Height value

Y (deep) le

Measured value of the internal standard l during calibration; depending on beta (deep) le; unit evaluation-dependent; e.g. Height value

Beta (deep) ie

Mass concentration of substance i in the working standard in Myg/l

Beta (deep) le

Mass concentration of internal standards in Myg/l

m (deep) il

Slope of the calibration line, unit dimensionless

b (deep) il

Axis section of the calibration straight line on the ordinate, unit dimensionless

These calibration functions are valid only for the concentration range covered therewith. They are also dependent on the operating state of the gas chromatograph (see VDLUFA (9)) and have to be checked regularly. For routine operation, at least one adjustment of the calibrating function in the form of a two-point calibration is to be carried out daily.

VIII.

Evaluation

VIII.1

Identification

The PCB congeners in the sample are identified by the retention times of the respective peaks in the sample gas chromatograms with the reference solutions measured under the same conditions or with those of a gas chromatogrammes of the reference solutions measured with the samples. the substances sought are compared with the sample extract (see DEV F2, section 11.1 (5)). In this case, corresponding peaks should occur as far as possible on two capillary columns of different polarity at the expected substance-specific retention times.
If a safe identification of individual PCBs with two capillary columns is not possible, for example in the case of highly loaded samples or disturbance by tetrachlorodiphenylmethanes, then another detection method may be used, for example the Mass spectrometry in the form of GC/MS coupling.

VIII.2

Quantification

The identified PCB congeners will be quantified using the internal standard procedure. The mass concentration beta (deep) i of the PCB i in mg/kg in the sewage sludge sample is calculated according to the following equation (2):

 Y (deep) i 
 ---------b (deep) il 
 Y (deep) l M (deep) i 
Beta (deep) i = -------------------- x -------- (2) 
 m (deep) il E   

This means:

Beta (deep) i

Mass concentration of the wanted PCB congener i in the sewage sludge sample in mg/kg

Y (deep) i

Measured value of the congener i in the measuring solution; unit evaluation-dependent; e.g. Height value

Y (deep) l

Measurement value of the internal standard l (decachlorobiphenyl) in the measuring solution; unit evaluation-dependent; e.g. Height value

M (deep) l

Mass of the internal standard added to the sewage sludge sample in Myg

E

Weight of the sewage sludge sample in g

M (deep) il, b (deep) il

See equation (1)

IX.

Quality assurance and quality control

The reliability of the results of this method must be secured by means of appropriate quality assurance and quality control measures. Some of the measures required shall be described, inter alia, by:

-American Chemical Society's Committee on Environmental Improvement (1983)	(12)
-Association of German Agricultural Research and Research Institutes, Section XI Environmental Analysis (1980)	(9)
-Association of German Agricultural Research and Research Institutes, Section XI Environmental Analysis (1984)	(10)
-Erickson (1986)	(15)
-Country Working Community of Water (1989)	(20)

In order to carry out the quality control in accordance with the references mentioned above, particular emphasis should be placed on the fact that:

a)

at least one method blind value per analysis series,

b)

high (> 80%) and reproducible recovery rates of PCB congeners, including internal standards,

c)

the performance of the measuring system (GC/ECD) is controlled and calibrated by regular measurements of control standards (e.g. through the guidance of control cards),

d)

all quality control measures are documented in a verifiable form and archived for a longer period of time.

X.

Blank values

In order to check the examination procedure, at least one method-blind value is to be measured for each analysis series. For this purpose, the entire process is carried out without a sample.
In the case of a significant blank value, the information values of calibration and sample measurement are to be corrected if the blank value cannot be further reduced by optimizing the GC separation or cleaning of the chemicals and equipment.

XI.

Indication of results

The results are formed as an arithmetic mean of two separate determinations (extractions). In this case, the mass concentrations of beta (deep) ij of the six PCB congeners are indicated individually in mg/kg of sewage sludge sample, rounded to 0.01 mg/kg.

XII.

Analysis Report

The report shall be based on this procedure and shall contain the following details:

a)

the identity of the sewage sludge sample,

b)

Information on sample pre-treatment, storage and preparation,

c)

complete indication of the procedure (aliquoting, dilution, GC conditions),

d)

Approach to the identification and quantification of individual PCBs,

e)

Indication of the results referred to in Section XI,

f)

any deviation from the examination procedure referred to above and indicating all the circumstances which may have influenced the result of the investigation.

1.3.3.2

Determination of polychlorinated dibenzodioxins and polychlorinated dibenzofurans

I.

Principles

The following determination procedure applies to the determination of selected PCDD and PCDF congeners in sewage sludge, as prescribed in accordance with Section 3 (6) of this Regulation.
It shall constitute an examination concept and shall be compiled in such a way that it combines the necessary and possible elements of an analytical method, with respect to and application of the method of analysis, in laboratories with analytical knowledge of experience and regular use of the analytical method. Implementation of the quality assurance and control measures for the implementation of the Abfclarification V will be provided with sufficiently safe results.

II.

Descriptive Summary

The freeze-dried sewage sludge sample is treated with (high) 13C-labelled PCDD and PCDF standards and extracted with toluene. The added standards and the PCDD/PCDF-congeners contained in the sample are largely freed from interfering accompanying substances, separated by capillary gas chromatography and subsequently mass spectrometrically determined by the following methods: MID (Multiple ion detection) technique, wherein the quantitation step is carried out according to the isotope dilution method.

III.

Equipment and chemicals

All equipment coming into contact with the sample and its solutions/extracts must be free of PCDD and PCDF within the limits of the detection limit of the procedure. All chemicals must have a degree of purity which allows the mass spectrometric determination of PCDD and PCDFs within the limits of the detection limit of the process. This is to be examined and guaranteed by regular blind-value investigations.

III.1

Usual laboratory equipment

III.2

Gas chromatograph for capillary chromatography

III.3

Mass spectrometer with evaluation unit

III.4

Gas-chromatographic separation columns

-

polar column, e.g. SP 2331 or SP 2330, 60 m

-

Non-polar column, e.g. DB-5, 25 m

III.5

Separating columns/packing materials for multistage column chromatography

III.6

Calibration substances

For the quantification to be carried out according to the isotope dilution method, a solution of (high) 13C-labeled PCDD and PCDF standards is used, which contains a PCDD or PCDF-isomer per homologue group.

IV.

Sample preparation (extraction and enrichment)

The multi-stage sample preparation can be quite different from the qualified and experienced examination sites in the individual stages. This is permissible, since the quality assurance and control accompanying the investigation ensures the comparability of the results obtained at the different examination sites. The following is an example of a tried-and-tested procedure (24) applied in many laboratories of investigation * 4):
50 g (even less in individual cases) of the freeze-dried and ground sample are admixed with the following (high) 13 C-labelled PCDD and PCDF: 5 ng each of 2,3,7,8-tetraCDD, 2,3,7,8-tetraCDF, 1,2,3,7,8-pentaCDD, 1,2,3,7,8-pentaCDF, 1,2,3,6,7,8-HexaCDD and 1,2,3,4,7,8-HexaCDF as well as 10 ng of 1,2,3,4,6,7,8-heptaCDD, 1,2,3,4,6,7,8-heptaCDF, octaCDD and octaCDF.
The sample is then extracted with toluene in a Soxhlet apparatus for 20 h. The toluene extract is concentrated to about 25 ml. In some cases, the extract can only be concentrated to about 40 ml, since there is already a galler-like mass.
The extract is then diluted with benzene to 100 ml. In the cases in which the extract can be concentrated only to about 40 ml, the mixture is made up to 200 ml with benzene. The values indicated in brackets in the following refer to the samples taken in 200 ml of benzene. 50 g (or 50 g) are placed in a chromatography column (60 × 4 cm). 75 g) of aluminium oxide and overlaid with 50 g of sodium sulphate. The extract is applied to the column and eluted with 300 ml (or 400 ml) of benzene and 300 ml (or 500 ml) of n-hexane/dichloromethane (98: 2). The eluates are discarded. The PCDD/PCDF fraction is then eluted with 300 ml of n-hexane/dichloromethane (1: 1). After a solvent change in n-hexane, the samples are chromatographed on a "mixed" column of silica gel (2 g), silica gel/NaOH (5 g), silica gel (2 g), silica gel/H (deep) 2SO (deep) 4 (10 g), silica gel (2 g) and silica gel/AgNO.sub.3 (deep) 3 (5 g). Elution is carried out with 300 ml of n-hexane. The eluate is concentrated to about 5 ml and then chromatographed on a column (30 × 2.5 cm), filled with BioBeads S-X3, with cyclohexane/ethyl acetate (1: 1) as eluent. The fraction of 100-160 ml contains the PCDD/PCDF. It is concentrated to a few milliliters, transferred into a 3 ml sample glass, the solvent is blown off in a stream of nitrogen, and the "residue" is taken up with about 50 ml of toluene. After carefully rinsing the wall of the sample coating with the solvent, 5 ng (high) 13C (deep) 6-1,2,3,4-tetraCDD are added and the volume of the sample solution is reduced to approximately 20 Myl.

V.

Gas chromatographic/mass spectrometry analysis (GC/MS)

The identification and quantification of the 17 PCDD/PCDF congeners to be used for the TCDD toxicity equivalent calculation is carried out using capillary gas chromatography and mass spectrometry detection. The VDI Directive 3499 (23) is to be applied in the implementation of this step.
-------
* 4) Variants without the hazardous working substance benzene are preferable to the procedure described here, provided that the accompanying substances which interfere with the PCDD/PCDF analysis are sufficiently separated and the comparability of the Results are saved.
-------

VI.

Quality assurance and quality control

In addition or amendment of the statements under 1.3.3.1/IX. This attachment shall be subject to the following provisions:

a)

The level and reproducibility of the recovery rates (WFR) of the (high) 13C-marked PCDD/PCDF standards for the selected separation steps must be checked regularly; for OCDD/OCDF, the WFR must be > 40%, for all other congeners > 70%.

b)

The performance of the measuring system (GC/MS) is to be monitored and calibrated by regular measurements (e.g. guidance of control cards).

VII.

Results of the results

The results are formed as an arithmetic mean of two separate determinations (extractions). In this case, the mass concentrations of the 17 PCDD/PCDF-congeners to be used for TCDD toxicity equivalent calculation are given individually in ng/kg sewage sludge dry matter, rounded to 1 ng/kg. For the calculation of the sum of the 2,3,7,8-TCDD toxicity equivalents (TE), the respective mass concentrations are multiplied by the following factors and the products are added.

2,3,7,8-TetraCDD	1.0
1,2,3,7,8-PentaCDD	0.5
1,2,3,4,7,8-HexaCDD	0.1
1,2,3,6,7,8-HexaCDD	0.1
1,2,3,7,8,9-HexaCDD	0.1
1,2,3,4,6,7,8-HeptaCDD	0.01
OctaCDD	0.001
2,3,7,8-TetraCDF	0.1
1,2,3,7,8-PentaCDF	0.05
2,3,4,7,8-PentaCDF	0.5
1,2,3,4,7,8-HexaCDF	0.1
1,2,3,6,7,8-HexaCDF	0.1
1,2,3,7,8,9-HexaCDF	0.1
2,3,4,6,7,8-HexaCDF	0.1
1,2,3,4,6,7,8-HeptaCDF	0.01
1,2,3,4,7,8,9-heptaCDF	0.01
OctaCDF	0.001

The value thus obtained shall be used to control the value to be checked in accordance with Article 4 (10) of this Regulation.

1.3.3.3

Literature

(1)	DIN (Hrsg.)	Calibration of analytical methods, evaluation of analytical results and linear calibration function for the determination of process parameters.
		DIN 38 402 Part 51, Beuth Verlag, Berlin 1986
(2)	DIN (Hrsg.)	Determination of the water content and the dry residue or the dry substance.
		DIN 38 414 Part 2, Beuth Verlag, Berlin 1985
(3)	DIN (Hrsg.)	Digestion with Königswasser for the subsequent determination of the acid-soluble fraction of metals,
		DIN 38 414 Part 7, Beuth Verlag, Berlin 1983
(4)	DIN (Hrsg.)	Determination of polychlorinated biphenyls.
		DIN 51 527 Part 1, Beuth Verlag, Berlin 1987
(5)	Expert group of water chemistry in the GDCh (Hrsg.)	German unit procedures for water, sewage and sludge investigation; jointly detectable substances (group F), gas chromatographic determination of low-volatility halogenated hydrocarbons and organochlorpesticides in water (F2).
		VCH publishing house. mbH, Weinheim 1985
(6)	Leschber, R., Taradellas, J., L' Hermite, P.L.	Polychlorinated Biphenyls (PCB), Determination in sewage sludge and related samples. Results of an interlaboratory comparison, Commission of the European Communities (Cost 681), Proceedings of a Round Table held in Langen, FRG 20-21 March 1985 Doc. SL/111/85, 96 S., Commission of the European Communities, DG XII, 1985
(7)	Taradellas, J., Muntau, H., Leschber, R.	Interlaboratory Comparisons of the Determination of PCBs as a Model Case for Organic Substances in Sludges. In: Organic Contaminants in Waste Water, Sludge and Sediments: Occurence, Fate and Disposal (D. Quaghebeur, I. Temmermann a. G. Angeletti, eds.), Proceedings of a Workshop held in Brussels, Belgium 26-27 October 1988 under the auspices of COST 641 and 681, pp. 81-93, Elsevier Applied Science, London-New York 1989
(8)	Beck, H., Mathar, W.	Analytical method for the determination of selected individual PCB components in food.
		Bundeshealthhbl. 28, No. 1, 1-12 (January 1985)
(9)	Association of German Agricultural Research and Research Institutes (Hrsg.)	Internal laboratory control in the residue analysis of chlorohydrocarbons. VDLUFA-Schriftenreihe, VDLUFA Verlag, Darmstadt 1980
(10)	Association of German Agricultural Research and Research Institutes (Hrsg.)	Framework concept for the routine analysis of polychlorinated biphenyls (PCBs). VDLUFA-Schriftenreihe, Heft 12, VDLUFA-Verlag, Darmstadt 1985
(11)	Ballschmiter, K., Schäfer, W., Buchert, H.	Isomer-specific identification of PCB-congeners in technical mixtures and environmental samples by HRGC-ECD and HRGC-MSD.
		Fresenius Z. Anal. Chem. 326 (1987) 253
(12)	American Chemical Society's Committee on Environmental Improvement (Hrsg.)	Principles of Environmental Analysis. Anal. Chem. 55 (1983) 2210
(13)	Buchholz, H., Carl, M., Beck, H., Tuinstra, L.G.M.Th.	Capillary gas chromatography "significant" chlorbiphenyls, a concept for routine analysis of polychlorinated biphenyls and its examination in a ring test.
		Farmer. Research 39 (1986) 1
(14)	Tuinstra, L.G.M.Th., Roos, A.H., Wells, D.E., Griepink, B.	Comparison of the Results for the Analysis of Individual Chlorobiphenyl Congeners in Various Interlaboratory Exercises.
		Microchem. Acta 1 (1989) 1
(15)	Erickson, M.D.	Analytical Chemistry of PCBs.
		Butterworth Publishers, Boston 1986
(16)	Erickson, M.D.	Analytical Method: The Analysis of By-product chlorinated Biphenyls in Commercial Products and Product Wastes, Revision 2.
		EPA Report No. 560 /5-85-010, Office of Toxic Substances, United States Environmental Protection Agency, Washington DC, May 1985
(17)	U.S. Environmental Protection Agency (Hrsg.)	EPA-Method 680. Determination of Pesticides and PCBs in Water and Soil/Sediment by Gas Chromatography/Mass Spectrometry.
		Office of Research and Development, Cincinnati, Ohio, November 1985
(18)	ISO (Hrsg.)	Soil Quality-Determination of organochlorine pesticides and polychlorinated biphenyls in soil.
		ISO/TC 190 /SC 2 N2 Rev. 3, Draft Proposal ISO/DP 10382, 1989
(19)	Kampe, W., Aldag, R., Zürcher, C., Jobst, H., LUFA Speyer	Investigation of relevant organic pollutants in sewage sludge.
		Research Report No. 103 03 521 on behalf of the Federal Environment Agency, Speyer 1990
(20)	Country-working Community Water (LAWA) (Eds.)	AQS-Analytical quality assurance. Framework recommendations of the Regional Working Group Water for water, sewage and sludge investigations.
		Erich Schmidt Verlag, Berlin 1989
(21)	Steinwandter, H.	Contributions to Silica Gel Application in Residue Analysis.
		Fresenius Z. Anal. Chem. 316 (1983) 493
(22)	Jensen, S., Renberg, L., Reutergardh, L.	Residue Analysis of sediment and sewage sludge for organochlorines in the presence of elemental sulfur.
		Anal. Chem. 49 (1977) 316
(23)	VDI (Hrsg.)	VDI 3499 Sheet 1 Measurement of polychlorinated dibenzodioxins and furans in the pure and crude gas of combustion plants using the dilution method. Determination in filter dust, boiler ash and in slag. Draft March 1990
(24)	Hagenmaier, H., Brunner, H., Knapp, W., Weberruß, U., Institut für Organische Chemie, University of Tübingen	Studies of selected soils and plants on dioxins and furans.
		Research report No. 107 01 010 on behalf of the Federal Environment Agency. Tübingen 1988

2

Floor

2.1

Sampling and preparation

For the sampling, the period after the harvest shall be selected until the next sludge application. At least one average sample shall be drawn from each uniformly managed plot (e.g. stroke, coupling) at the size of up to one hectare. On larger plots of land, samples from parts of approximately one hectare are to be taken from parts of up to three hectares, with uniform soil characteristics and the same management. For an average sample, at least 20 stitches are required up to the machining depth. The stitches are to be spread evenly over the surface.
The average sample is dried in the air, if necessary crushed, sieved (< 2 mm), mixed and partial samples according to DIN 38 414, part 7 * 1) are comminuted to a particle size of 0.1 millimeter.
To accelerate the drying process, drying can be carried out at 40 ° C. in a drying cabinet.

2.2

Conduct of investigations

At least two parallel investigations shall be carried out for each examination parameter, and the arithmetic mean of the two values shall be indicated as a result. Equivalent methods are permitted.

2.2.1

Determination of heavy metals

Digestion and determination of the heavy metals are carried out from the air-dry average sample.
The samples are drawn up in accordance with the DIN standard 38 414, part 7 (January 1983 edition) * 1) (royal water breakdown).
The measurement is carried out in the case of lead, cadmium, chromium, copper, nickel and zinc according to DIN standard 38 406, part 22 (March 1988 edition) * 1), for mercury according to DIN-Norm 38 406 Part 12 (July 1988 edition) * 1).
The results of the heavy metal determiners shall be expressed in milligrams per kilogram of dry mass (105 degrees C).

2.2.2

Determination of plant nutrients

The contents of plant-available phosphate, potassium and magnesium are determined in the air-dry sample with the methods * 5 customary in agricultural fertilizer consulting.
The results shall be expressed in milligrams per kilogram of dry mass (105 degrees C).

2.2.3

Determination of pH

The determination of the pH value is to be carried out in accordance with DIN-standard 19 684 /T 1 (1977) * 1). Before any further lamming, the pH-value measurement can be carried out using a mobile method. The accuracy difference to the DIN method can be no more than 0.2 pH units.

2.2.4

Determination of the clay content

The determination of the clay content is to be carried out in accordance with DIN standard 18 123 (1983) * 1).

3

Overrun of limit values

The excess of one of the permitted levels according to § 4 (8), (10), (11) and (12) shall be established in principle if the determined contents are

-

of the heavy metal by more than 5%

-

of the respective PCB congeners by more than 25%

-

of halogen organic compounds (AOX) by more than 10%

-

on TCDD toxicity equivalent of more than 25%

above the corresponding limit values.
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* 5) See e.g. VDLUFA-Schriftenreihe, Heft 15 (s. Section 5).
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4

Quality assurance and control

The investigative bodies are obliged to ensure the reliability of the analytical results by means of appropriate measures for quality assurance and quality control * 6). This includes, among other things, the successful participation in ring trials of the competent federal state.

5

Announcements of expert bodies

The notices referred to in sections 1 and 2 of the German Patent Office (German Patent Office) in Munich (German Patent Office) have been established in an archive-proof way. The following have been published:

-

the DIN standards at Beuth-Verlag GmbH, Berlin and Cologne,

-

The "German Unit Processes for Water, Wastewater and Sludge Investigation", the Section for Water Chemistry of the Society of German Chemists, published by Verlag Chemie, Weinheim/Bergstrasse, Germany.

-

the manual of the agricultural experiment and examination methodology (method book) published by J. Neumann-Neudamm in Melsungen.

6

Further documents

Association of German Agricultural Research and Research Institutes (Hrsg.): Investigation of sewage sludge and soil samples on the content of heavy metals and nutrients lt. German Federal Ordinance of 25 June 1982, VDLUFA-Schriftenreihe, Heft 15, VDLUFA-Verlag, Darmstadt 1986.
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* 6) See e.g. AQS-Analytical quality assurance. Framework recommendations of the Regional Working Group Water for water, sewage and sludge investigations.
Edited by: LAWA, E. Schmidt Verlag, Berlin 1989.
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Figure 1
Scheme of PCB determination in sewage sludge
(Content: non-representable image,
Fundstelle: BGBl. I 1992, 929)
Table 1

Investigation methods for sewage sludge
Lfd. No.	Parameters	Method of investigation (s) * 1)	Matrix/Sample Preparation
1	PH value	DIN 38 414, part 5 (September 1981 edition)	Original sample
2	Dry residue	DIN 38 414, part 2 (November 1985 edition)	Original sample
3	Loss of ignition (organic substance)	DIN 38 414, part 3 (November 1985 edition)	Dry residue
4	Total nitrogen	DIN 19 684, part 4 (February 1977 edition) (distillation process)	Original sample
5	Ammonium nitrogen	DIN 38 406, part 5 (October 1983 edition)	Original sample
6	Lead	DIN 38 406, part 6 (May 1981 edition)	Royal waterfront * 2)
		DIN 38 406, part 22 (March 1988 edition)
7	Cadmium	DIN 38 406, part 19 (July 1980 edition)	Royal waterfront * 2)
		DIN 38 406, part 22 (March 1988 edition)
8	Calcium	DIN 38 406, part 3 (September 1982 edition)	Royal waterfront * 2)
		DIN 38 406, part 22 (March 1988 edition)
9	Chrome	DIN 38 406, part 10 (June 1985 edition)	Royal waterfront * 2)
		DIN 38 406, part 22 (March 1988 edition)
10	Potassium	DEV Method E 13 (5). Delivery 1968)	Royal waterfront * 2)
		DIN 38 406, part 22 (March 1988 edition)
11	Copper	DIN 38 406, part 22 (March 1988 edition)	Royal waterfront * 2)
12	Magnesium	DIN 38 406, part 3 (September 1982 edition)	Royal waterfront * 2)
		DIN 38 406, part 22 (March 1988 edition)
13	Nickel	DIN 38 406, part 22 (March 1988 edition)	Royal waterfront * 2)
14	Phosphorus	DIN 38 414, part 12 (November 1986 edition)	Royal waterfront * 2)
		DIN 38 406, part 22 (March 1988 edition)
15	Mercury	DIN 38 406, part 12 (July 1988 edition)	Royal waterfront * 2)
16	Zinc	DIN 38 406, part 8 (October 1980 edition)	Royal waterfront * 2)
		DIN 38 406, part 22 (March 1988 edition)
17	Adsorbed, organically bound halogens (AOX)	Din 38 414, part 18 (November 1989 edition)	Dry residue

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* 1) Reference sources see section 4.
* 2) The dry residue according to DIN 38 414, part 7 (January 1983 edition) * 1). Unofficial table of contents

Annex 2 Waste water treatment plant

 Source of the original text: BGBl.  I 1992, 931-934   
Name and address of the operator: Location: ............................... 
..................................  Date: .............................. 
..................................  Tel.: .............................. 
..................................  Fax: ............................... 
  
 Delivery note 
 pursuant to § 7 Abfclarification V 
This delivery note is from the operator of the waste water treatment plant 
to be kept for 30 years. 
Name and address of the user: 
........................................................................ 
........................................................................ 
  
We will be in/in the month/s ............. 19 ...  ..... cbm sewage sludge 
with a dry substance content of ...%, which corresponds to a 
Quantity of ... t dry mass, on parcels no.  ....., 
Gemarkung ............, Size .......... (hectare) 
...... 
..... apply. 
..... by ............................................................ 
 (name and address of the authorised third party) 
  
 can be brought up/brought up. 
Current land use: ....................................................... 
The ground investigation of .............................. (Analyse-No.: ........) 
  
..... does not exceed the permitted levels of heavy metals 
 . 
..... has a partial overshoot of the permitted contents 
 Heavy metals result. 
  
The sewage sludge was treated as follows: 
..... biologically ..... chemically ..... thermally ..... long-term 
 stored 
..... decontaminating ..... other treatment ............................ 
  
The Sewage Sludge Investigation from the ............... (Analyse-No.: .......) 
..... did not exceed the permitted levels of pollutants. 
..... has a partial overshoot of the permissible pollutant contents 
 . 
The soil/sewage sludge tests have the following results: 
1) Floor: 
ph value ........ 
Soil type i.S.v.  § 4 (8) and  12 Abfclarification V ........ 
  
The soil contains on average: 
------------------------------------------------------------------------ 
 Mg/ 100 g dry matter 
------------------------------------------------------------------------ 
Phosphate (P (deep) 2O (deep) S): I 
Potassium oxide (K (deep) 2O): I 
Magnesium (MG): I 
------------------------------------------------------------------------ 
 mg/kg dry matter 
------------------------------------------------------------------------ 
 I Maximum contents according to.  Section 4 (8) 
 I Abfclarification V 
------------------------------------------------------------------------ 
Lead: I 100 
Cadmium: I 1,5 (1 according to § 4 (8) sentence 2) 
Chromium: I 100 
Copper: I 60 
Nickel: I 50 
Mercury: I 1 
Zinc: I 200 (150 according to § 4 (8) sentence 2) 
  
2) sewage sludge: 
The sewage sludge has the following pH value: ........... 
  
The sewage sludge contains on average: 
------------------------------------------------------------------------ 
 I a) Nutrient-I b) Nutrient- 
 I hold in I contents in 
 I der Frisch-I der Trocken- 
 I substance in I substance in 
 I% I% 
------------------------------------------------------------------------ 
Organic substance: I I 
Total nitrogen (N): I I 
Ammonium nitrogen (NH (deep) 4-N): I I 
Phosphate (P (deep) 2O (deep) 5): I I 
Potassium oxide (K (deep) 2O): I I 
Calcium oxide (CaO): I I 
Magnesium oxide (MgO): I I 
------------------------------------------------------------------------ 
 Sludge Dry Mass (m (deep) T) 
------------------------------------------------------------------------ 
 I limit values according to.  Section 4 (11) and (12) 
 I Abfclarification V 
------------------------------------------------------------------------ 
Lead: I 900 
Cadmium: I 10 (5 pursuant to § 4 (12) sentence 2) 
Chromium: I 900 
Copper: I 800 
Nickel: I 200 
Mercury: I 8 
Zinc: I 2,500 (2000 according to § 4 para. 12 
 I sentence 2) 
AOX: I 500 
------------------------------------------------------------------------ 
 Sludge Dry Mass (m (deep) T) 
------------------------------------------------------------------------ 
 I limit values according to.  Section 4 (10) 
 I Abfclarification V 
------------------------------------------------------------------------ 
PCB* 1) No.  I 
 28: I 138: I 0.2 mg PCB/kg m (deep) T je 
 52: I 153: I component 
101: I 180: I 
------------------------------------------------------------------------ 
 ng TE/kg m (deep) T 
------------------------------------------------------------------------ 
PCDD, PCDF* 2): I 100 ng TE/kg m (deep) T 
 I 
  
It is confirmed that the sludge of our wastewater treatment plant 
in accordance with the above information in accordance with the Sewage Sludge Ordinance 
of 15 April 1992 (BGBl.  912) and the competent authority of the competent authorities 
Directive on recovery introduced by the supreme authority 
of sewage sludge in agriculture of .......... 
can be. 
  
 ............................................................... 
 (Signature of the operator of the waste water treatment plant) 
  
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* 1) Systematic numbering of the PCB components according to the 
Rules of the International Union for Reine and Applied Chemistry 
(IUPAC). 
* 2) According to the calculation rule in Annex 1 to the Abfclarification V. 
  
 Confirmation of delivery 
 pursuant to § 7 (2) sentence 1 of the Abfclarification V 
  
We have today ....... cbm sewage sludge with a 
Dry substance content of ......%, which corresponds to ....... t 
Dry matter, submitted in accordance with the above information. 
  
 ............................................................... 
 (Signature of the operator of the waste water treatment plant) 
  
 Confirmation of the application of the sewage sludge 
 pursuant to § 7 (2) sentence 3 Abfclarification V 
  
I have passed today to me by .................. ......... 
Sewage sludge according to the preceding claims.  The 
Section 6 of the Sewage Sludge Regulation shall not be allowed to apply 
exceeded. 
  
 ............................................................... 
 (Signature of the purchaser/farmer) 
  
(The form is required with 6 copies.)