Sewage Sludge Ordinance

Original Language Title: Klärschlammverordnung

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Read the untranslated law here: http://www.gesetze-im-internet.de/abfkl_rv_1992/BJNR009120992.html

Sewage sludge Ordinance (German) German Ausfertigung date: 15.04.1992 full quotation: "sewage sludge Ordinance of 15 April 1992 (BGBl. I p. 912), most recently by article 5 paragraph 12 of the Act of February 24, 2012 (BGBl. I p. 212) is changed" stand: last modified by article 5 para 12 G v. 24.2.2012 I 212 for more information on the stand number found in the menu under instructions this regulation serves the implementation of Directive 86/278/EEC of 12 June 1986 on the protection of the environment and in particular the floors for the use of sewage sludge in agriculture (OJ EC No. L 181, p. 6).
Footnote (+++ text detection from: 1.7.1992 +++) (+++ official note of the standard authority on EC law: implementing EWGRL 278/86 (CELEX Nr: 31986 L 0278) +++) input formula on the basis of § 15 para 2 of the waste management Act, August 27, 1986 (BGBl. I S. 1410, 1501) enacted the Federal Minister for environment, nature conservation and nuclear safety, in agreement with the Federal Minister for food, agriculture and forestry and with the Federal Minister of health, on the basis of § 11 paragraph 2 sentence 3 , Paragraph 3 set 4 of this Act enacted the Federal Minister for environment, nature conservation and nuclear safety: § 1 scope of application (1) this regulation has to note who operates 1 waste water treatment plants and emits sludge to apply on soils used for agriculture or landscaping or wants to leave, 2 brings up sludge on agricultural or horticultural shared floors or wants to bring up.
(2) the provisions of fertilizer law remain unaffected.
(3) the concerned work that are below the thresholds referred to in this Regulation as far as possible. The floor limit values referred to in the regulation were set for the specific conditions of agricultural sewage sludge utilization. General cultivation restrictions or limitations otherwise can not derive from reaching or exceeding the values.

Article 2 definitions (1) waste water treatment plants are plants for the treatment of waste water, regardless of developing size and type of treatment. Small wastewater treatment systems are systems with multiple chambers to the treatment of domestic sewage with a dirty water inflow of less than 8 cubic meters per day. Water wells are no waste water treatment plants within the meaning of regulation without drain.
(2) sewage sludge is also drained or dried or treated in any other form in the treatment of sewage in wastewater treatment systems including mud related incurred further sewage treatment plants. Raw mud is mud that untreated waste water treatment plants is taken. The dehydration of raw sludge is not considered to be treatment of sewage sludge. Sludge falling in sewage is considered sewage sludge in the sense of this regulation. Sewage sludge within the meaning of this regulation are considered to be also sewage sludge compost and sewage sludge mixture. Sewage sludge mixtures are mixtures of sewage sludge with other appropriate materials tables 11 and 12 of the fertilisers regulation in amended according to annex 2. Sewage sludge composts are composted sewage sludge mixture.
(3) the purposes of this regulation, plant species, which are grown on arable land and their vegetative Teile are intended for an animal feed are field lining. The cultivation of maize do not include field forage cultivation within the meaning of this regulation.

Article 3 conditions for applying must (1) sewage sludge on agricultural or horticultural used soils only so that the common of good is not affected and the application of available soil nutrients and organic matter as well as the site and growing conditions is aligned according to type, amount, and time on the nutrient needs of the plants, taking into account applied,. In addition the provisions of fertilizer legislation shall apply for the application of sewage sludge.
(2) the operator of a waste water treatment plant is obliged to investigate containing lead, cadmium, chromium, copper, nickel, mercury and zinc soil tests a point designated by the competent authority before the initial application of sewage sludge on used agricultural or horticultural soils.
(3) the soil investigations referred to in paragraph 2 can be repeated at intervals of 10 years. The competent authority arranges in coordination with the competent authority of agricultural trade that the soil surveys at shorter intervals are to repeat, if according to the result of carried sewage sludge and soil investigations and taking into account the amount of application, as well as other causes of heavy metal pollution exceeding the values referred to in article 4, paragraph 8 is to get. She may limit the additional soil sampling to certain units and heavy metals.
(4) sewage sludge may be applied only if the soil has been studied on the pH value, the percentage of plants available phosphate, potassium and magnesium. The operators of the waste water treatment plant has the costs for the implementation of this soil survey to wear.
(5) sewage sludge may be only submitted to apply agricultural or horticultural use soil or applied there if, at intervals of no longer than six months samples of the sludge by an authority specified by the competent authority on the levels of lead, cadmium, chromium, copper, nickel, mercury and zinc, on the sum of organic halogen compounds as adsorbed organic halogens (AOX), total and ammoniacal nitrogen , Phosphate, potassium, magnesium and the dry residue, organic matter, the basic active substances and pH are examined. The competent authority may extend the investigation to other ingredients. She can shorten the distance of the investigations of the sewage sludge up to two months. While she may limit investigations on individual heavy metals.
(6) sewage sludge may be are only submitted to apply agricultural or horticultural use soil or there applied, when prior to the initial application, and thereafter at intervals of not longer than two years samples of sewage sludge on the contents of the organic persistent pollutants - examined polychlorinated biphenyls and polychlorinated dibenzodioxins and dibenzofurans. Paragraph 5 sentence 3 shall apply accordingly. The investigation is carried out by one of the bodies designated by the competent authority.
(7) the operator of a waste water treatment plants have the sampling and investigations under paragraphs 2, perform 3, 5 and 6 of the statement in the annex 1 to this regulation, or to perform.
(8) in the case of applying sludge from septic of a farm on our own plots of land, the provisions are paragraphs 2 to 7 do not apply. Sludges from such plants are to analyze before first applying to the parameters referred to in paragraph 5. The results are to send immediately by the operator of the system of the competent authority and the competent agricultural trade.
(9) in the case of the application of sewage sludge from waste water treatment plants for the treatment of household sewage, urban waste water or waste water with much lower pollution levels and a smaller expansion size as 1 000 EW investigations can be omitted after an initial examination referred to in paragraph 2 with the consent of the competent authority for paragraphs 3 and 6. The testing should be according to paragraph 5 at intervals of no longer than two years; the competent authority can shorten the distance of the investigations up to six months or extend up to 48 months, and extend the study to other ingredients.
(10) for small wastewater treatment systems of individual households in the area referred to in article 3 of the Unification Treaty, investigations are to carry out the paragraphs 2 to 7 until 31 December 1998 only on the orders of the competent authority.
(11) a sentence 1 and paragraph 6 is set 3 referred to in paragraph 2, paragraph 5 to determine if the applicant has the required expertise, independence, reliability, and technical facilities. The determination is carried out by the competent authority of the country in which the applicant has his place of business, and is valid for the entire Federal territory; no place of business in Germany, the country is responsible, in which the activity is to be exercised primarily pursuant to paragraphs 2, 5 and 6. The provision can be equipped with a proviso of the cancellation, a time limit, with conditions, the reservation conditions and requirements. The competent authority may require a nationally active applicant that he had a valid accreditation of compliance with the requirements of DIN EN ISO/IEC 17025:2005 (to refer at the Beuth-Verlag GmbH, 10772 Berlin, and archive terms secured laid down in the German national library in Leipzig) submits, relates to the parameters and examination procedure in accordance with Appendix 1. Procedure under that provision can be handled via a single point. The examination of the application for determination of a place must be completed within three months; section 42a paragraph 2 sentence 2 to 4 of the Administrative Procedure Act applies.
(12) equal recognition in another Member State of the European Union or another Contracting State to the agreement on the European economic area rules are referred to in paragraph 2, paragraph 5 sentence 1 and paragraph 6 sentence 3 equal. The examination of the application for determination in accordance with paragraph 2, paragraph 5 sentence 1 and paragraph 6 sentence 3 are evidence from another Member State of the European Union or another Contracting State to the agreement on the European economic area the same domestic evidence if from them indicating that the applicant fulfils the relevant requirements of paragraph 11 set 1 or on the basis of their objective in essentially comparable requirements of the exhibition State. Evidence of recognition within the meaning of sentence 1 or other evidence pursuant to sentence 2 shall be provided the competent authority prior to commencement of activities in the original or copy. A certification of the copy, as well as a certified German translation may be required.

§ Banned 4 prohibitions of application of and restrictions (1) which is applying raw sludge or mud from other waste water treatment plants for the treatment of household sewage, urban waste water or waste water with similar low pollution on agricultural or horticultural use soils.
(2) the application of sewage sludge on vegetable - and fruit-growing areas is prohibited. On plots of land, used also for growing field vegetables the growing field vegetables is forbidden in the year of application of sewage sludge and the following year.
(3) on plots of land used for growing field feed or to the cultivation of sugar beets, as far as the sugar beet leaf, fed, a sewage sludge applied just before planting with subsequent low applicable training is allowed. The cultivation of silage and green maize, the sludge prior to the seed in the ground is to work.
(4) the application of sewage sludge on Permanent grasslands is prohibited.
(5) the application of sewage sludge on forestry use soil is prohibited.
(6) the application of sewage sludge to agricultural or horticultural use soil in protected areas, national parks, national nature monuments, nature monuments, protected landscape elements and legally protected habitats within the meaning of section 30 of the federal nature conservation Act is prohibited, unless it is an exception under section 5.
(7) the application of sewage sludge on soil in zones I and II by water conservation, as well as on soils in the area of the shore edge trim up to a width of 10 metres is prohibited. Further provisions for water protection areas for water legislation remain unaffected.
(8) the application of sewage sludge on agricultural or horticultural shared floors is forbidden, when according to § 3 par. 2 or 3 results from the soil surveys, that the levels of below mentioned heavy metals exceed at least one of the following values (milligrams per kilogram of dry matter): lead cadmium 100 1.5 chrome 100 copper 60 nickel 50 mercury 1 zinc 200 at floors, which are classified in the bottom estimate as light soils and their clay content is less than 5 per cent or its examination in accordance with article 3 Paragraph 4 a pH of more than 5 and less than 6 has revealed, is an application of sewage sludge also then banned, if exceeding the heavy metals cadmium and zinc values (milligrams per kilogram of dry matter): cadmium 1 zinc 150 (9) the application of sewage sludge on agricultural or horticultural shared floors is forbidden unless sought a target value of pH 5 or less as part of proper management for these floors or a pH of 5 or less in the investigation is determined according to § 3 para 4. Floors, whose target is proper management, about pH 5 in order to require the on liming with Düngekalken falls below this value and a sewage sludge application. When calculating the amount of lime, the then-to-be basic effective shares in sewage sludge are taken into account.
(10) the application of sewage sludge on agricultural or horticultural shared floors is forbidden, when according to § 3 par. 6 resulting from the sewage sludge investigations, 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 matter for the components number 28, 52, 101, 138, 153, 180;
-Polychlorinated Dibenzodioxins/dibenzofurans (PCDD/PCDF) 100 nanograms TCDD toxicity equivalents (in accordance with the formula in annex 1) per kilogram of sludge dry matter.
(11) the application of sewage sludge on agricultural or horticultural shared floors is forbidden if according to § 3 para 5 results from the sewage sludge investigations, that the sum of the halogen-organic compounds, expressed as a sum parameter for AOX, exceeds 500 milligrams per kilogram mud dry.
(12) the application of sewage sludge on agricultural or horticultural shared floors is forbidden, if according to § 3 para 5 resulting from sewage sludge investigations, that the contents of the following heavy metals exceed at least one of the following values (milligrams per kilogram of sludge dry matter): lead 900 cadmium 10 copper chrome 900 800 nickel 200 mercury 8 Zinc 2 500 in soils, which are classified in the bottom estimate as light soils and their clay content is less than 5 per cent or whose examination pursuant to § 3 para 4 one has resulted in more than 5 and less than 6 pH, insert 1 following values for cadmium and zinc in set are: cadmium 5 zinc 2 000 (13) in the production of sewage sludge compost and sewage sludge mixtures refer to the levels of pollutants according to the paragraphs 10, 11 and 12 on the used sludge and the aggregates before mixing as well as the produced compost or the produced mixture. When applying a mixture produced by sewage sludge using the Schadstoffracht product of according to paragraphs 10, 11 and 12 permitted pollution levels and the according to § 6 ABS. 1 permissible application amount resulting from must not be exceeded.
(14) sewage sludge may be stored only on or near the boarding area, insofar as this is necessary for the application.

In agreement with the competent nature conservation agency in the particular case, a permit for the application of sewage sludge on arable land in protected areas, national parks, national nature monuments, nature monuments, protected landscape elements and legally protected habitats within the meaning of section 30 of the federal nature conservation Act § 5 grant derogations that competent authority may.

§ Must be applied within by three years no more than 5 tonnes dry matter in sludge per hectare 6 floors referred application quantity (1) in article 1. Sewage sludge composts may be placed on the inside of 3 years up to 10 tons of dry matter per hectare pollutant levels in sewage sludge compost do not exceed half of the heavy metals permitted pursuant to § 4 paragraph 12 and half of permitted pursuant to § 4 paragraph 10 levels of organic pollutants.
(2) in the case of applying a mixture using sewage sludge refers to the application of allowance on the used sludge and not the mixture referred to in paragraph 1. The proportion of sewage sludge must be proven by the supplier and made known to the user. Regardless of § 4, paragraph 13, sentence 2 shall apply.

§ 7 proof obligations (1) no later than two weeks prior to the placing of the sludge displays the operators of the waste water treatment plant or a responsible third party of authority responsible for the application area and the agricultural technical authority of the intended application by sending a copy of the completed delivery to the model in annex 2 to this regulation.
(2) the operator of sewage treatment plant indicated the time of the levy of sewage sludge on the delivery note and passes this to the carrier. The delivery is to carry during transport in the vehicle. The delivery and the application of sewage sludge is to be confirmed by the customer.
(3) if the customer and the carrier keep per a copy of the delivery note, depending on a further copy sends the carrier on the authority responsible for the wastewater treatment plant and that for the application area, the original operator of the wastewater treatment plant. This one has the original 30 years from the date of delivery to store and present the competent authorities upon request. The possibilities of electronic data processing can be used for the implementation of paragraphs 1 and 2 and of sentence 1.
(4) the obligations to the paragraphs 1 to 3 shall also apply if operators of waste-water treatment plants bring the sewage sludge on own land or bring up.
(5) the authority responsible for the application area may waive in consultation with the agricultural technical authority for certain waste-water treatment plants the ads referred to in paragraph 1.
(6) in the case of movements of sewage sludge in the scope of the waste Act the obligations of the operator apply the paragraphs 1 to 4, for the owner of the sludge, which spends it in the scope of the waste management act or can spend the sewage treatment plant after.
(7) operators of waste-water treatment plants keep records include the following information: 1 created a mud Engen and the mud Straits provided to agriculture (in dry matter of tonnes of), 2.
Properties of the sludge in accordance with article 3 par. 5, 3. type of treatment of the sewage sludge, 4. name and address of the recipients of the sludge, stroke-specific label the application area, assigned floor piece number, 5. results of the soil investigations, classified according to beats and sorted by floor number.
The operators of waste-water treatment plants pass this information until March 31 of the following year for the previous calendar year to the authorities responsible for the enforcement of sewage sludge Ordinance professionally.
(8) the authorities responsible for the implementation of the sewage sludge Ordinance provide the information under paragraph 7 No. 1 to 3 August 31st of next year for the previous calendar year to the Supreme Land authorities. The countries undertake the summarized data to the Federal Minister for environment, nature conservation and nuclear safety. The Federal Minister for environment, nature conservation and nuclear safety created a summary report for the Commission of the European communities on the basis of the information provided by the countries every four years, for the first time in 1991.
(9) of the obligations according to the paragraphs 1 to 7, the operators of waste-water treatment plants for the treatment of household sewage, urban waste water or waste water with much lower pollution levels and a smaller expansion size as 1,000 EW are excluded.
(10) on the recycling of sewage sludge to which apply the provisions of this regulation, the provisions of the regulation with the exception of section 2 para 1 No. 2 and of article 23 no. 2 of the regulation found no application.

Section 8 application plan agricultural trade authorities of the countries or third parties authorized by this have a year to create an application plan of the sewage sludge applied in the course of the calendar year.

§ 9 rude in the sense of article 69, paragraph 1 number 8 of the circulatory economic law that offences (1) who intentionally or negligently sludge without the required soil analyses raises 1. contrary to article 3, paragraph 4, sentence 1, 2. contrary to article 3, paragraph 5, sentence 1 or paragraph 6 is off set 1 sewage sludge without the prescribed examination to apply or brings up, 3. contrary to article 3, paragraph 8, sentence 2 not analyzed sludge , 4. contrary to article 3, paragraph 9, sentence 2 sewage sludge without the prescribed examination to apply emits or brings up, 5. contrary to article 3, paragraph 10, an enforceable order not, not properly or in time to comply with, 6 contrary to article 4, paragraph 1, 2 sentence 1, paragraph 4, 5 or 6 set 1 first half-sentence or paragraph 7 to 11 mud brings up, 7 contrary to section 4, paragraph 2, sentence 2 , in connection with paragraph 3 sentence 1, grows there called plants or not deep turning edited the ground, 8 contrary to section 4 paragraph 3 sentence 2 works in the sewage sludge before the seed in the ground, 9 contrary to § 4 paragraph 12 raises sewage sludge on agricultural or horticultural use floors, 10 contrary to § 4, paragraph 13, sentence 2 sewage sludge mixes raises, 11 contrary to § 4 paragraph 14 sludge on or nearby warehousing application area or 12 contrary to § 6 more than the mentioned Amounts of dry matter in sludge, sewage sludge composts or a mixture, using sewage sludge brings up.
(2) any person within the meaning of article 69, paragraph 2, point 15 of the circulatory economic law is who intentionally or negligently 1 contrary to section 3, paragraph 8, sentence 3 not or not timely findings leading to the competent authorities, 2nd contrary to § 7 paragraph 1 that displays not or not timely application of sewage sludge, 3. contrary to article 7, paragraph 2, sentence 2 not carrying the delivery during transport in a vehicle , 4. delivery pursuant to annex 2 to this regulation does not, not properly or not completely fills or a copy of the delivery note contrary to section 7, paragraph 3, sentence 2 kept 30 years or presents him to the competent authority upon request not to test or 5. contrary to article 7, paragraph 7 does not, not properly or not fully register or not or not timely forwards the information.

Article 10 entry into force, expiry this regulation enters into force on the first day of the third on the calendar month following announcement.

Concluding formula the Federal Council has approved.

Appendix 1 sampling, sample preparation and analysis of sewage sludge and soil (site of the original text: BGBl. I, 1992, 917-930) 1 sludge 1.1 sampling for the investigations provided for in § 3 of sewage sludge is sampling according to DIN 38414, part 1 (issue November 1986) * 1) is applied in the State of sewage sludge like this on the farmland.
To ensure of representative results are bulking up in the following way to produce: the date of the examination each five litres are before from at least five different duties of sewage sludge to remove sludge and to unite in a suitable container (E.g. aluminium) to the aggregate sample. Sampling should be several days apart if possible.
From the carefully mixed aggregate sample a subset of is taken, which is sufficient to ensure four parallel investigations for all prescribed study parameters.
The subset is bottled in a well sealed, suitable container (E.g. aluminium) and promptly delivered to the investigating body.
1.2 sample preparation the sludge sample transactions to study is mixed directly sustained prior to taking a subsample. If there is a risk of segregation, the subsample is during mixing.
For all scan settings are determined from the dry, a subsample is to remove, which is at least sufficient to ensure four parallel investigations.
For freeze drying a subsample is taken from also, enough at least to four parallel provisions for making the section 1.3.3.1 and 1.3.3.2.
Freeze drying is to perform to avoid evaporation losses of the substances to be examined. In particular, it is sure that the trial not antaut during freeze-drying. Sewage sludge with high water content should part are drained before freeze-drying by centrifugation. The separate Zentrifugat will contain no particles.
1.3 conduct of investigations when working with fresh and freeze dried sewage sludge are the usual safety rules for working in microbiological laboratories * 2) to comply with. If the test results are not affected, a subset of the fresh or freeze dried mud for the corresponding investigations can be sterilized if necessary (E.g. due to 30minütiges heating the sample at 70 degrees C).
At least two parallel investigations are run for each scan settings, and as a result is the arithmetic mean of the two values to specify. Equivalent methods are approved.
1.3.1 the prescribed examinations of this parameter determination of heavy metals, nutrients, pH, dry residue, loss of glow and the adsorbed organically-bound halogen (AOX) are performed according to the methods listed in table 1.
Determination of basic active substances I. applicable in sewage sludge, the calcium and magnesium in basic effective form (E.g. as oxide, hydroxide and carbonate) contain 1.3.2 scope and field of application which is method.
II. principle of the substance is associated with acid in solution and the hyperacidity back titrated. The basic active substances are specified as % CaO.
---* 1) reference source see section 5 * 2) see E.g. laboratory safety. Preliminary recommendations for dealing with pathogenic micro-organisms and for the classification of micro-organisms and pathogens to the dangers arising in dealing with them in: Federal Health Gazette 24 No. 22 of 30 October 1981, 347-359 - III chemicals III. 1 hydrochloric acid solution, c (HCL) = 0.5 mol / l III. 2 sodium hydroxide solution (NaOH) c = 0.25 mol / l III. 3 Phenolphthaleinlösung w (phenolphthalein) = 1% in ethanol (96% = w)
IV. usual laboratory equipment V. implementation * 3) V. 1 sample preparation of according to DIN 38 414 part 2 * 1) dried at 105 degrees C and according to DIN 38 414 part 7 * 1) crushed and homogenized sample are precisely weighed on an analytical balance 2 g to 1 mg, placed in a 200 ml volumetric flask with 100 ml hydrochloric acid after section III. transferred 1. The flask is left standing until the end of the main reaction in the cold. It is carefully heated and five minutes in boiling, so that no leak of hydrochloric acid. After the end of solving is cooled, filled up to the mark with water, shake and filtered.
V. 2 method Foerster 50 ml (A) of the salt acid filtrate (according to section V. 1) are pipetted into a 200 ml volumetric flask and with the addition of Phenolphthaleinlösung to section III. 3 with caustic according to section III. 2 titrated. The still slightly acidic liquid is boiled for the removal of carbon dioxide and titration continued until the occurrence of turbidity (spent lye amounts = X ml).
Then is cooled down, filled with water up to the mark, shaken and filtered. In 100 ml filtrate = 0.25 g substance is (amount of liquor consumed y = ml) led to end of the titration.
VI. calculation of basic active substances W(Tief)BAS % CaO content is calculated according to the following formula: (A - 0.5 B) = x W(Tief)BAS = X C (50 - y) X 1,402 2 B = (x + 2 y) (ml) - A:
Submission to hydrochloric acid solution in B: of ml (factor of 1.00) - consumption of caustic soda solution in x: of ml (factor of 1.00) - consumption of sodium hydroxide solution until the occurrence of turbidity - y: consumption on sodium hydroxide solution after the filtration - C: conversion factors C(tief)1 1,402 for CaO C(tief)2 = = 2,502 for CaCO(tief)3 1.3.3 1.3.3.1 determination of polychlorinated biphenyls I. determination of polychlorinated biphenyls (PCBs), the polychlorinated dibenzodioxins (PCDDS) and of polychlorinated dibenzofurans (PCDFS) principles the subsequent investigation is for precautionary reasons according to § 3 para 6 suitable prescribed provision of the six selected PCB congeners in sewage sludge.
It is based on the standards DIN 51 527 part 1 (4) * 1), DIN 38 407 part 2 (DEV F2, 1985 draft) * 1) (5) and ISO/TC 190/SC 3 N2 Rev. 3 (18), as well as on the results of the interlaboratory tests which were carried out by the working party 2 of concerted action COST 681 in the European Community (6, 7). In addition, the newer literature was included (8, 9, 10, 11, 13, 14, 15, 19).
The procedure describes proven practices which may be applied only by analysts or under their supervision who have experiences in the trace analysis by gas chromatography and provide the necessary measures for quality assurance and control (see section IX).
---* 3) see method book vol. II of VDLUFA 'Investigation of fertilizers'.
-Prescribed steps may be derogated from only, if the Gas-chromatographic separation of the PCB congeners by disturbing koeluierende substances is so disrupted that it is not possible to make a reliable identification/quantification. In these exceptional cases it can be useful to repeat preset cleaning steps or making additional other cleaning methods. Still, it may be necessary here to use a mass spectrometric detector.
Hydrocarbons chlorinated to the separation of PCBs from some, like for example p, p-DDT, dieldrin, Heptachlor epoxide, HCH-isomers, and others can, if necessary, be used as additional cleaning step a silica gel column (see, E.g., 15, 18, 19 and 21).
Because the procedure described here is based on the limits of the German, both the Aliquotierungs - and dilution volumes need to be changed in the determination of very low levels of PCBs as also the given dimensions on internal standard.
II. short description the freeze dried sewage sludge sample after addition of internal standard with n-hexane in the Soxhlet extracted. In the extract possibly contained PCB congeners are largely free of disturbing accompanying materials by cleaning steps, separated by capillary gas chromatography and electron capture detector (ECD) to determine (see diagram in Figure 1).
III. chemicals all chemicals must exhibit a degree of purity, which allows the determination of PCB components within the framework of the limit of detection of the procedure. This is to check through regular blind value investigations and to ensure, where appropriate, additional cleaning measures.
III. 1 solvent for the residue analysis of n Dodecane, n-hexane and isopropyl alcohol, if necessary, further cleaned, E.g. via a highly efficient distillation column re distilled.
III. 2 water, demineralised III. 3 desiccant III. 3.1 sodium sulfate, anhydrous sodium sulfate is, if necessary, for the cleaning and drying at for at least two hours 550 ° C in muffle furnace annealed.
III. 3.2 magnesium perchlorate III. 4 tetrabutylammonium hydrogen sulfate (TBA) III. 5 sodium Sulfit III. 6 3.39 g tetrabutylammonium hydrogen sulfate are TBA-bisulfite reagent into a 100 ml volumetric flask on 0.01 g accurately weighed, dissolved in demineralized water and filled with water. The solution into a 250 ml separating funnel three times with 20 ml of n-hexane extracts and saturated with 25 g of sodium sulphite. The solution should be stored no longer than a month.
III. 7 silver nitrate III. 8 packing materials for the column chromatography III. 8.1 aluminum oxide alumina W 200, basic, or neutral, activity Super 1 Rijo, or equivalent, is 16 hours at 150 degrees C or two hours at 400 degrees C dried.
89 g of dried aluminum oxide be 11 g water and shaken in a sealed bottle so long until all lumps are gone. The mixture is kept in a sealed bottle for at least 16 hours prior to first use.
III. 8.2 silica silica gel 60, 0.063 0.200 mm (70-230 mesh), E.g. Merck quality no. 7754, or equivalent, is 16 hours at 200 degrees C dried, cooled in a desiccator over magnesium perchlorate and kept there for 14 days.
III. 8.3 silver nitrate/silica gel mixture are 10 g of silver nitrate in 40 ml of water solved and batches in 90 g activated silica gel according to section III. 8.2-given. The mixture is shaken so long until there are no lumps and then heated in an oven within five hours from 70 degrees to 120 degrees C.
The mixture is heated to enable 15 hours at 125 degrees C, cooled in a desiccator over magnesium perchlorate, stuffed in a Brown bottle and kept there for a maximum 14 days.
III. 9 gases III. 9.1 carrier gas helium or hydrogen, each with a volume fraction >-99.99%.
III. 9 2 help gases gas mixture consisting of 95 parts by volume argon and five volumes of methane; alternative nitrogen, each with a volume fraction > 99.99%. Nitrogen, clean and oil-free for pushing down small extract volumes.
III. 10 calibration and reference substanzen III. 10.1 PCB 2,4,4'-Trichlorbiphenyl PCB 28 individual components 2, 2 ', 5, 5'-Tetrachlorobiphenyl PCB 52 2, 2 ', 4, 5, 5'-Pentachlorbiphenyl 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'-Heptachlorbiphenyl PCB 180 Decachlorbiphenyl PCB 209 (internal standard) stock solutions are the individual components of a mixture containing each component be replaced by E.g. 10 Myg/ml in hexane. The work standards of Stammlösung(en) with n-hexane produced as by diluting, yields a linear display of the electron capture detector over the chosen workspace under the given Gas chromatographic conditions. In General, levels 2 Myg/l are sufficient for this up 20 Myg/l.
An equal mass of Decachlorbiphenyl as internal standard is added to all labor standards. This mass should be sized so that the measuring signal of the internal standard in the linear work range is larger than the measuring signal of the individual PCB components of labour standards with the highest PCB content. For example, a concentration of internal standard of 20 Myg/l might be enough with a working area of 2 Myg/l up to 20 Myg/l and an injection volume of 1-2 Myl.
The sludge sample is placed prior to extraction with so much internal standard, that the measuring signal of the internal standard in the sample solution for section V. 2.1.2 or V. 2.2 is larger than the measuring signal of the individual PCB components in this solution, but not more than ten times of that is. An addition of 500 ng Decachlorbiphenyl results in a corresponding content in the solution of 20 Myg/l in the approach described here.
III. 10.2 technical PCB mixtures to the peak pattern recognition and for determining the separation efficiency of the Gas chromatographic system technical PCB mixtures used. In addition to the individual products Chlorphen(Hoch)R A30, A40, A50 and A60 or the corresponding Arochlorgemischen(Hoch)R is A40 for the above purpose in particular a mixture of Chlorphen(Hoch)R and A60 used E.g. with a concentration of 2 Myg/ml.
IV. equipment all devices coming with the sample and their solutions/extracts in touch must exhibit a degree of purity, which allows the determination of PCB components within the framework of the limit of detection of the procedure. This is to check through regular blind value investigations and to ensure, where appropriate, additional cleaning measures.
IV. 1 usual laboratory equipment IV. 2 freeze plant IV. 3 Kapillargaschromatograph with electron capture detector (ECD) IV. 4 Gas chromatographic separation column DIN 51 527 see part 1 * 1), section 5.3 (4) and DEV F2 * 1), section 7.2.2 (5).
IV. 5 columns for the liquid chromatographic cleaning glass columns of different lengths (E.g. 150 to 250 mm) with an internal diameter of 6 mm bottom leaking to a point about 40 mm length and at the top of E.g. 50 mm fitted with a reservoir, length 20 mm I.d..
In the following columns, the elution behaviour of PCBs on the column with a mixture of six PCB components and Decachlorbiphenyl is regularly, but at least to check with each new lot of the packing material.
IV. 5.1 aluminum oxide column to a chromatography column section IV. 5 is provided with a plug of glass wool and aluminium oxide was with 2 g in n-hexane (see section III. 8.1) filled.
IV. 5 2 silver nitrate/silica gel column to a glass column section IV. 5 is provided with a plug of glass wool with a 5 mm-high layer of anhydrous sodium sulphate, with 2 g silver nitrate/silica gel mixture referred to in section III. 8.3 and filled it again with a 5 mm-high layer of anhydrous sodium sulfate. The column must be made fresh before every cleaning.
V. sample preparation V. 1 extraction
2 grams of freeze-dried and according to DIN 38 414 part 7 (3) * 1) with 500 ng Decachlorbiphenyl as internal standard be put into an analysis mill of crushed and homogenized sludge in an extraction tube (where appropriate before cleaned) accurately weigh a 1 mg, (see section III. 10.1) and extracted with n-hexane (E.g. 70 ml) in the Soxhlet Extractor. The duration of extraction is so calculated that around 80-100 extraction cycles take place. The extract is, if necessary, filtered through gentle distillation, if necessary, after the addition of some n Dodecane (E.g. 100 Myl of a solution of 20 Myg/Myl n Dodecane in n-hexane) narrowed to about 5 ml, in a 10 ml volumetric flask transferred and populated with n-hexane.
V. 2 cleaning of extract to the separation of PCBs from disturbing accompanying materials are described here are two equivalent procedures (see diagram in Figure 1).
(a) a two-stage approach, which includes the removal of sulfur and sulfur-containing compounds with TBA and an alumina column chromatography.
(b) a single-stage cleaning with a silver nitrate/silica gel separator column.
Both practices are sufficient usually for slightly polluted samples.
V. 2.1 cleaning with TBA and alumina V. 2.1.1 removal of sulfur and sulfurous compounds (22) 2 ml of the extract referred to in section V. 1 or possibly some other appropriate are prorated basis in terms with 1 ml of isopropanol and 1 ml TBA bisulfite reagent and vigorously shaken at least two minutes. Should then no crystalline precipitate formed have so often each 100 mg of sodium sulfite are added and shaken until a crystalline precipitation remains. Shake again two minutes after the addition of 5 ml of water. The hexane phase is separated and the aqueous phase after extracted twice with little n-hexane. The United organic phases are dried with sodium sulphate and filtered off. Wash the sodium sulphate twice with little n-hexane, and the entire n-hexane phase is gently pushed with nitrogen to 1 ml.
V. 2.1.2 aluminium oxide column the n hexane phase reduced to 1 ml according to section V. 2.1.1 is quantitatively using a pipette on the aluminum oxide separation column washed with n-hexane according to section IV. abandoned 5.1. The residue container after washed with 0.5 ml of n-hexane. The hexane is abandoned with the pipette onto the surface of the Pack if the meniscus of the solution just seeps. This rinsing process is repeated twice. Then the column is described as above batches with 5 ml n-hexane or a volume referred to in section IV. 5 has been determined, eluted. The eluate is narrowed at room temperature in a nitrogen stream gently to about 3 ml and populated for GC analysis in the volumetric flask with n-hexane to 5 ml.
V. 2.2 cleaning with silver nitrate/silica gel 2 ml of the extract referred to in section V. 1, or possibly some other appropriate prorated basis in terms referred to in section IV to be on the silver nitrate/silica column washed with n-hexane. abandoned 5 2.
If the meniscus of the extract in the surface of the Pack seeps, 40 ml be given sufficient volume batches n-hexane or another to complete the PCB Elution on the column. The whole of the eluate is narrowed down gently to about 3 ml and populated for GC analysis in the volumetric flask with n-hexane to 5 ml.
VI. Gas chromatographic identification and quantification of the six PCB congeners in the purified extract determined with capillary gas chromatography and electron capture detection. The separation efficiency of the GC system must be optimized to achieve a sufficient resolution of PCB 28 and PCB 31 components. (The optimization of the GC working conditions see 51 527 part 1 * 1) DIN, 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 to ensure the identification of PCB components with two capillary columns of different polarities. Remains to ensure that no interference between the PCB components 101 and o, p'-DDE and alpha-endosulfan, respectively, as well as between PCB 138 and p, p'-DDT occur.
The sludge sample in addition to PCB contains also Tetrachlordiphenylmethane (such as E.g. ugilec 141), the columns a large part of the corresponding isomers also resides in the eluate and can interfere with the identification and quantification of the PCB component 153. A mass spectrometric detector should be used to properly quantify of this component in this case (see, for example, 11, 15, 16, 17, 19).
VII. calibration the Gas chromatographic separation system is calibrated in the linear range of the ECD. This advantageous multi component solutions are used as working standards (see section III. 10.1).
The linear calibration functions of the individual PCB components are based on DIN 38 402 part 51 * 1) (1) calibration distributed through at least five equidistant over the working area following concentrations: the labour standards which is endowed with internal standard are injected in rising concentrations in the gas under the same conditions as in the measurement of the samples. J received readings Y(Tief)IEJ be used in relation to the measured values of the internal standard Y(Tief)Lej. As the underlying readings mass concentrations beta(Tief)IEJ and beta(Tief)Lej. The calibration function (1) are calculated by linear regression from these conditions: Y(Tief)IE Beta(Tief)IE - m(tief)il x - = + b(tief)il (1) Y(Tief)Le beta(Tief)Le this mean: Y(Tief)IE reading of the PCB (i) for the calibration. subject to beta(Tief)IE; Unit subject to evaluation; for example, height value Y(Tief)Le reading of the internal standard l calibration; subject to beta(Tief)Le; Unit subject to evaluation; E.g. altitude value beta(Tief)IE mass concentration of the substance (i) in the work standard in Myg / l beta(Tief)Le mass concentration of internal standard in Myg / l m(tief)il slope of the calibration line, unit dimensionless b(tief)il intercept of the calibration lines on the ordinate, unit dimensionless these calibration functions apply only to the concentration range thus covered. You are also dependent on the operational state of the gas chromatograph (see VDLUFA (9)) and must be checked regularly. For the routine operation, at least an adjustment of the calibration function, in the form of a two-point calibration is perform.
VIII. evaluation VIII. 1 identifying the PCB congeners in the sample are identified by the retention times of the peaks in the sample Gaschromatogrammen are compared with the reference solutions measured under the same conditions or those of a Gaschromatogrammes of the sample extract increased with the searched substances (see DEV F2, section 11.1 (5)). This, each matching peaks should occur during the expected substance-specific retention times as possible on two capillary columns of different polarities.
A secure identification of individual PCB with two capillary columns is not possible, E.g. with strongly contaminated samples or interference from Tetrachlordiphenylmethane, then, if necessary, another proof technique to be used, E.g. mass spectrometry in the form of the GC/MS coupling.
VIII. 2 quantify the identified PCB congeners be quantified with the procedure of the internal standard. The mass concentration of PCB (i) in mg/kg in the sludge sample beta(Tief)i is calculated by the following equation (2): Y(Tief)i --b(tief)il Y(Tief)l M(Tief)i beta(Tief)i = - x - (2) m(tief)il E herein mean: beta(Tief)i mass concentration of selected PCB congeners i in the sludge sample in mg/kg Y(Tief)i reading of the congeners i in the test solution; Unit subject to evaluation; for example, height value Y(Tief)l reading of the internal standard (Decachlorbiphenyl) l in the measuring solution. Unit subject to evaluation; E.g. altitude value M(Tief)l mass of the internal standard, which the sludge sample added to equation (1) weight of the sludge sample in g M(Tief)IL, was b(tief)il in Myg E see IX. quality assurance and quality control that is reliability of the results of this method to secure suitable measures of quality assurance and quality control. Individuals the necessary measures, inter alia described at:-American Chemical Society Association's Committee on environmental improvement (1983) (12) - Association of German agricultural research and research institutions, section XI environmental analysis (1980) (9) - German agricultural research and research institutions, section XI environmental analysis (1984) (10) - Erickson (1986) (15) - land Association of water (1989) (20) for the implementation of quality control in accordance with the mentioned references among others especially value that is up to , that: a) per analysis series at least one method blank value is to measure b) high (> 80%) and reproducible recovery rates of PCB congeners including the internal standards are achieved, c) the performance of the Meßsystems (GC/ECD) is controlled by regular measurements of control standards and calibrated (E.g., by management of control charts), d) all quality control measures in the form of verifiable are documented and long-term archived.
X. dummy values
Control of the examination procedure, at least one method blank value to be measured is per series of analyses. To do this, the entire process without sample is performed.
A significant blind value the information assets of calibration and measurement of samples are correct, if the blank value is not reduced by optimizing the GC separation or purification of chemicals and equipment.
XI. indication of the results the results are formed as arithmetic mean value of two separate provisions (extractions). While the mass concentrations are specified individually rounded to 0.01 mg / kg beta(Tief)IJ of the six PCB congeners in mg/kg sewage sludge sample.
XII. analysis report should refer to this procedure and include the following details: a) identity of the sludge sample, b) details the sample preparation, storage, and processing, c) full indication of the approach (factoring, dilution, GC conditions), d) procedure for the identification and quantification of individual PCB, e) specifying the results referred to in section XI, f) any deviation from the above mentioned investigation and all circumstances , which may have influenced the investigation result.
1.3.3.2 determination of polychlorinated dibenzodioxins and polychlorinated dibenzofurans I. principles the following determination procedure is to apply mandatory determination of selected PCDD and PCDF congeners in sewage sludge for precautionary reasons according to § 3 par. 6.
It represents a concept of investigation and is compiled so that it summarizes the necessary and possible elements of a method of analysis in their consideration and application in trace analytical experienced laboratories and regular implementation of measures to ensure the quality and for the implementation of the horticulture sufficiently reliable results will get control.
II. short description is the freeze dried sewage sludge sample with (high) 13C-markierten PCDD and PCDF standards and extracted with toluene. The added standards and the PCDD/PCDF congeners contained in the sample, if necessary, are largely free of disturbing accompanying materials, separated by capillary gas chromatography and then peaklist after the MID(Multiple ion detection) technique determines where quantification step is performed according to the isotope dilution method.
III. equipment and chemicals should be free all devices coming with the sample and their solutions/extracts in touch within the framework of the limit of detection of the procedure of PCDD and PCDF. All chemicals must have a purity that allows the mass spectrometric determination of PCDDS and PCDFS in the framework of the limit of detection of the procedure. This is to check through regular blind value investigations and to ensure.
III. 1 usual laboratory equipment III. 2 gas chromatograph of capillary GC 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. a solution of (high) 13C-markierten PCDD-is 5 columns/packing materials for multi-tiered column chromatography III. 6 calibration substances for the quantification of isotope dilution method to be implemented and PCDF standards used, each containing a PCDD - or PCDF isomer per Homo lodge group.
IV. sample preparation (extraction and enrichment) the multi-stage sample preparation varies quite at the qualified and experienced investigative bodies in the different stages. This is allowed because the comparability of the results obtained in the different investigative bodies is secured with accompanying the study quality assurance and quality control. An example of a proven and applied in many research laboratories how to (24) is laid down in the following * 4): 50 g (in some cases of less) of freeze-dried and ground sample is spiked with following (high) 13 C-labelled PCDD and PCDF: 1,2,3,4,6,7,8-HeptaCDD 5 ng 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, 1,2,3,4,6,7,8-HeptaCDF , OctaCDD and OctaCDF.
The sample is extracted then 20 h with toluene in a Soxhlet apparatus. The toluene extract is narrowed to about 25 ml. In some cases, the extract only on about 40 ml can be restricted because there is already a gelatinous mass.
The extract is then diluted with benzene to 100 ml. In the cases where the extract only on about 40 ml can be pushed down, is populated with benzene up to 200 ml. The values given in the following in brackets refer to the samples that have been recorded in 200 ml benzene. In a chromatography column (60 x 4 cm), 50 g (or 75 g) are filled with aluminum oxide and via switches with 50 g of sodium sulphate. The extract is applied to the column and eluted with 300 ml (or 400 ml) benzene and 300 ml (or 500 ml) n hexane/Dichloromethane (98:2). The eluate are discarded. Then, the Group of the PCDD/PCDF is eluted with 300 ml of n hexane/Dichloromethane (1:1). After changing the solvent in n-hexane, the samples on a "mixed" column of silica gel (2 g), silica gel/NaOH (5 g), silica gel (2 g), Kieselgel/H(tief)2SO(tief)4 (10 g), silica gel (2 g) and Kieselgel/AgNO(tief)3 (5 g) will collect. With 300 ml n-hexane is eluted. The eluate is restricted to approximately 5 ml and then passed to a column (30 x 2.5 cm), filled with BioBeads S-X 3, with cyclohexane/ethyl acetate (1:1) as solvent reservoir chromatographiert. The Group of 100-160 ml contains the PCDD/PCDF. It is restricted to a few millilitres in a specimen jar transferred 3 ml, the solvent in the flow of nitrogen blown off and the "residue" recorded toluene with circa 50 Myl. Once the wall of the sample jar with the solvent has been rinsed thoroughly, 5 ng (hoch)13C(tief)6-1,2,3,4-TetraCDD be added to and reduces the volume of the sample solution to approximately 20 Myl.
V. gas-chromatography/mass spectrometric analysis (GC/MS) identification and quantification of the 17 PCDD/PCDF congeners to be used for TCDD toxicity equivalent calculation is done with capillary gas chromatographic and mass spectrometric detection. When performing this step, the VDI guideline 3499 (23) is to apply.
---* 4) variants, benzene coming off without the dangerous working material, are preferable shown here how if the accompanying substances disturbing the PCDD/PCDF analysis be sufficiently separated and the comparability of the results is guaranteed.
---VI. quality assurance and quality control in addition to or amendment of the designs on 1.3.3.1/IX. this annex the following definitions shall apply: a) height and repeatability of recovery rates (WFR) of (high) 13C-markierten PCDD/PCDF-standards for the selected separation steps are regularly to check for OCDD/OCDF have the WFR at > 40% for all other congeners at > 70%.
(b) the performance of the measurement system (GC/MS) is to control through regular measurement and calibration (E.g. management of control charts).
VII. information of the results the results are formed as the arithmetic mean of two separate provisions (extractions). While the mass concentrations of 17 of the TCDD toxicity equivalent calculation are specified individually rounded to 1 ng/kg PCDD/PCDF congeners to be used in ng/kg sewage sludge dry. To calculate the sum of the 2,3,7,8-TCDD-Toxizitätsäquivalente (TE) are multiplied by the respective mass concentrations with the following factors and products 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 this resulting value is to be used for the control of the value to be checked according to § 4 paragraph 10 of this regulation.
1.3.3.3 literature (1) DIN (eds.) calibration of analytical methods, evaluation of analysis results and linear calibration function for the determination of Verfahrenskenngrößen.
DIN 38 402 part 51, Beuth Verlag, Berlin 1986 (2) DIN (eds.) determination of moisture content of dry residue and dry matter.
DIN 38 414 part 2, Beuth Verlag, Berlin 1985 (3) DIN (eds.) digestion with aqua regia to the subsequent determination of säurelöslichen content of metals, DIN 38 414 part 7, Beuth Verlag, Berlin 1983 (4) DIN (eds.) determination of poly chlorinated biphenyls.
DIN 51 527 part 1, Beuth Verlag, Berlin 1987 (5) section water chemistry in the Gesellschaft Deutscher Chemiker (ed.) German unit procedures for water, wastewater and sludge investigation; Together detectable substances (Group F), Gas chromatographic determination of difficult volatile halogenated hydrocarbons and Organochlorpestiziden in water (F2).
VCH Verlagsges. mbH, Weinheim 1985 (6) Leschber, R., Taradellas, j., L'hermite, P.L.. polychlorinated bi phenyls (PCB), determination in sewage sludge and related samples. Results of comparison of interlaboratory Commission of hero of the European Communities (cost 681), proceedings of a round table in Langen, FRG 20-21 March 1985 doc. SL/111/85, 96 p., Commission of the European communities, DG XII, 1985 (7) Taradellas, j., Makwana, 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 sediment: 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. new analytical methods for the determination of selected PCB components in foods.
Bundesgesundhbl. 28, no. 1, 1-12 (January 1985) (9) Association of German of agricultural development and research establishments (ed.) internal laboratory control in the residue analysis of chlorinated hydrocarbons. VDLUFA series, VDLUFA Verlag, Darmstadt 1980 (10) Association of German agricultural development and research establishments (ed.) framework for the routine analysis of polychlorinated biphenyls (PCBs). VDLUFA publication series, no. 12, VDLUFA-Verlag, Darmstadt 1985 (11) Ballschmiter, k., Schäfer, W., Banu, 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 (eds.) principles of environmental analysis. Anal. Chem. 55 (1983) 2210 (13) Buchholz, H., Carl, M., Beck, H., Tuinstra, L.G.M.Th capillary gas chromatography of Chlorbiphenyle "significant", a concept for the routine analysis of Polychlorierter biphenyls and its test in the multicentre trial.
Ourthe. 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.
Mikrochem. 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 of chlorinated bi phenyl in commercial products and product wastes, revision 2. EPA report No. 560/5-85-010, Office of toxic substances, U.S. environmental protection agency, Washington, DC, May 1985 (17) U.S. Environmental Protection Agency (ed.) EPA method 680th 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 (ed.) soil quality – determination of organochlorine pesticides and polychlorinated bi phenyl in soil.
ISO/TC 190/SC 2 N2 Rev. 3, draft proposal ISO/DP 10382, 1989 (19) Kampe, W., Abbey, R., Zurich, C., Jobst, H., LUFA Speyer investigation of relevant organic pollutants in sewage sludge.
Research report No. 103 03 521 in the German Federal of environmental agency, Speyer 1990 (20) water (LAWA) Working Group (ed.) AQS - analytical quality assurance. Guidelines of working group of water for water, wastewater and sludge analysis.
Erich Schmidt Verlag, Berlin 1989 (21) Sanjay, 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 (ed.) VDI 3499 sheet 1 measurement of polychlorinated dibenzo - furans in the pure and raw gas from combustion plants using the dilution method. Determination of fly ash, bottom ash and slag. Draft March 1990 Knapp (24) Hagenmaier H., Brunner, H., W., Weber, Ruß, U., Institute of organic chemistry, University of Tübingen on investigations of selected soils and plants, dioxins and furans.
Research report No. 107 01 010 in the German Federal of environmental agency. Tübingen 1988 2 ground 2.1 sampling and preparation for sampling is the period after the harvest until the next application of sewage sludge to choose. Every uniformly managed land (E.g. shock, coupling) at least a sample of average is up to one hectare size. On larger plots are samples from parts of approximately one hectare, to take up to three hectares in native soil and same management parts. For a sample of the average, at least 20 punctures are required to the processing depth. The punctures are to distribute evenly over the surface.
The average is air dried, if necessary crushed, sieved (< 2 mm), mixed and partial samples according to DIN 38 414, part 7 * 1) crushed to a grain size of 0.1 mm.
To accelerate the drying process can be dried at 40 degrees C in an oven.
2.2 investigations for every scan settings are to perform at least two parallel investigations, and as a result is the arithmetic mean of the two values to specify. Equivalent methods are approved.
2.2.1 determination of heavy metals digestion and determination of heavy metals made in the air dry average sample.
The samples are according to DIN 38 414, part 7 (Edition January 1983) standard * 1) open-minded (aqua regia digestion).
The measurement is made with lead, cadmium, chromium, copper, nickel and zinc according to the DIN standard 38-406, part 22 (Edition March 1988) * 1), for mercury after the DIN 38 406 part 12 (Edition July 1988) * 1).
The results of the heavy metal determinations are to specify in milligrams per kilogram of dry matter (105 degrees C).
2.2.2 determination of plant nutrients to the levels of plant-available phosphate, potassium and magnesium in the air dry sample with the methods of agricultural fertilizer * 5) determined.
The results shall be given in milligrams per kilogram of dry matter (105 degrees C).
2.2.3 determination of pH is the determination of the pH value according to the DIN standard 19 684 / T 1 (1977) * 1) perform. The pH measurement with a mobile process can be done before any further loading Schlammung. The accuracy difference to the DIN method must be maximum 0.2 pH units.
2.2.4 determination of sound is the determination of the sound according to the DIN standard 18 123 (1983) * 1) perform.
3 exceeded of the limits exceeding one permitted levels according to § 4 paragraph 8, 10, 11 and 12 is generally proven if the determined levels - of each heavy metal by more than 5% - of individual PCB congeners by more than 25% - halogen organic compounds (AOX) to more than 10% - are on TCDD toxic equivalent to more than 25% above the relevant limit values.
---* 5) see E.g. VDLUFA series, issue 15 (see section 5).
---4 quality assurance and control the investigation agencies are required, the reliability of the analytical results through appropriate measures for quality assurance and quality control * 6) to secure. This includes among other things the successful participation in interlaboratory studies of the competent State.
5 notices of expert bodies the notices referred to in sections 1 and 2 expert bodies are laid down with the German Patent Office in Munich archive terms secured. There appeared: - the DIN at the Beuth-Verlag GmbH, Berlin and Cologne, - the "German standard method for water, wastewater and sludge investigation", the water chemistry of the society of German chemists in the publishing group chemistry, Weinheim/mountain road, the manual of agricultural research and methodology (method book) published by j. Neumann Neudamm in Melsungen.
6 more documents Association of German of agricultural development and research establishments (ed.): investigation of sewage sludge and soil samples on the content of heavy metals and nutrients according to the sewage sludge Ordinance of the Federal Government by June 25, 1982, VDLUFA series, issue 15, VDLUFA-Verlag, Darmstadt 1986.
---* 6) see E.g. AQS - analytical quality assurance. Guidelines of working group of water for water, wastewater and sludge analysis.
Ed.: LAWA, E. Schmidt Verlag, Berlin 1989 - figure 1 schema of PCB determination in sewage sludge (content: not displayable picture, site: BGBl. I, 1992, 929) table 1 methods for sludge item No. No. parameter Untersuchungsmethode(n)*1) matrix/sample preparation 1 pH DIN 38 414, part 5 (Edition September 1981) original sample 2 dry residue DIN 38 414, part 2 (issue November 1985) original sample 3 loss on ignition (organic matter) DIN 38 414 , Part 3 (November 1985 issue) dry residue 4 total nitrogen DIN 19 684, part 4 (Edition February, 1977) (distillation processes) original sample 5 ammonium nitrogen DIN 38 406, part 5 (Edition October 1983) original sample 6 lead DIN 38 406, part 6 (Edition may 1981) aqua regia digestion * 2) DIN 38 406, part 22 (Edition March 1988) 7 cadmium DIN 38 406, part 19 (Edition July 1980) aqua regia digestion * 2) DIN 38 406 , Part 22 (issue of March 1988) 8 calcium DIN 38 406, part 3 (September 1982) aqua regia digestion * 2) DIN 38 406, part 22 (March, 1988 Edition) 9 chrome DIN 38 406, part 10 (Edition June 1985) aqua regia digestion * 2) DIN 38 406, part 22 (Edition March 1988) 10 potassium DEV procedures E 13 (5. delivery 1968) aqua regia digestion * 2) DIN 38 406, part 22 (March, 1988 Edition) 11 copper DIN 38 406 , Part 22 (Edition March 1988) aqua regia digestion * 2) 12 magnesium DIN 38 406, part 3 (September 1982) aqua regia digestion * 2) DIN 38 406, part 22 (Edition March 1988) 13 nickel DIN 38 406, part 22 (Edition March 1988) aqua regia digestion * 2) 14 phosphorus DIN 38 414, part 12 (issue November 1986) aqua regia digestion * 2) DIN 38 406, part 22 (Edition March 1988) 15 mercury DIN 38 406 , Part 12 (Edition July 1988) aqua regia digestion * 2)
16 zinc DIN 38 406, part 8 (Edition October 1980) aqua regia digestion * 2) DIN 38 406, part 22 (Edition March 1988) 17 adsorbed, organically-bound halogen (AOX) DIN 38 414, part 18 (issue November 1989) dry residue - * 1) sources see section 4 * 2) of dry residue according to DIN 38 414, part 7 (Edition January 1983) * 1).

Appendix 2 wastewater treatment plant site of the original text: BGBl. I, 1992, 931-934, name and address of the operator: place:... Datum: .............................
.................................. Tel.: ..............................
.................................. Fax: ...............................
Delivery in accordance with § 7 German this delivery is by the operators of the waste water treatment plant for 30 years to be kept.
Name und Anschrift des Anwenders:
........................................................................
........................................................................
We are in the / in the month (s)... 19... cbm sludge with a dry matter content of... %, which corresponds to a lot of... t dry matter, floor piece No...., municipal..., size... ... Submit (hectares).
... bring it on.
..... durch ............................................................
(Name and address of the appointed third party) deliver / get up.
Current land use:...
The ground survey of the... (Analysis-no.:...)
... showed no exceeding permitted levels of heavy metals.
... has resulted in a partially exceeded of permitted levels of heavy metals.
The sludge was treated as follows:... organic... chemically... thermal... long-term stored... disinfect... other treatment...
The investigation of the sludge from the... (Analysis-no.:...)
... showed no exceeding of permissible pollutant levels.
... has revealed some exceeding of permitted emissions levels.
The soil / sludge investigations have the following results: 1) soil: Ph...
Soil type within the meaning article 4 paragraph 8 or 12 German...
The soil contains an average: mg / 100 g of dry matter - phosphate (P(tief)2O(tief)S): I potassium oxide (K(tief)2O): I magnesium (MG): I - mg/kg dry matter - I maximum levels gem. § 4 paragraph 8 I horticulture - lead: I 100 cadmium: I 1.5 (1 according to § 4 section 8 set 2) chrome: I 100 copper: I 60 Nickel: I 50 mercury: I 1
Zinc: I 200 (150 according to § 4, paragraph 8, sentence 2) 2) sewage sludge: the sludge has following Ph:...
The sludge contains in the Middle: - I a) nutrient I b) nutrient I levels in I levels in I of the fresh I of dry I substance in I substance in I % I % - organic matter: I total nitrogen (N): I ammonium nitrogen (NH(tief)4-N): I I phosphate (P(tief)2O(tief)5): I I potassium oxide (K(tief)2O): I I calcium oxide (CaO) : I I
Magnesiumoxid (MgO): I I
------------------------------------------------------------------------
mg/kg Schlamm-Trockenmasse (m(tief)T)
------------------------------------------------------------------------
I Grenzwerte gem. § 4 Abs. 11 und 12
I AbfKlärV
------------------------------------------------------------------------
Blei: I 900
Cadmium: I 10 (5 nach § 4 Abs. 12 Satz 2)
Chrom: I 900
Kupfer: I 800
Nickel: I 200
Quecksilber: I 8
Zink: I 2.500 (2.000 nach § 4 Abs. 12
I Satz 2)
AOX: I 500
-------------------------------------------------- ----------------------
mg/kg Schlamm-Trockenmasse (m(tief)T)
------------------------------------------------------------------------
I Grenzwerte gem. § 4 Abs. 10
I AbfKlärV
------------------------------------------------------------------------
PCB*1) Nr. I 28: I 138: I 0.2 mg PCB/kg m(tief)T per 52: I 153: I component 101: I 180: I of ng TE/kg m(tief)T - PCDD, PCDF * 2): I 100 ng TE/kg m(tief)T I it is confirmed, that mud our waste water treatment plant in accordance with the information provided above in accordance with the sewage sludge Ordinance of 15 April 1992 (Federal Law Gazette I p. 912) and the recycling of sewage sludge in agriculture policy introduced by the Supreme authority of the country by the... can be recycled.
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(Unterschrift des Betreibers der Abwasserbehandlungsanlage) - * 1) systematic numbering of the PCB components according to the rules of the International Union of pure and applied chemistry (IUPAC).
* 2) in accordance with the calculation rules in annex 1 to the horticulture.
Confirmation of the levy referred to in section 7, paragraph 2, sentence 1 German we have today... cbm sludge with a dry matter content of... %, which corresponds to... given t dry matter, in accordance with the information provided above.
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(Signature of the owner of the wastewater treatment plant)
Confirmation of the application of sewage sludge in accordance with article 7, paragraph 2, sentence 3 horticulture today I me by... on... passed sewage sludge in accordance with the above findings applied. The application of allowance according to § 6 of the sewage sludge Ordinance will not be exceeded.
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(Signature of the customer 's/farmer)
(The form is required with 6 copies.)