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COMMISSION OF THE EUROPEAN COMMUNITIES, QUAGHEBEUR, TEMMERMAN ANDANGELETTI, COORD; Organic contaminants in waste water, sludge and sediment,occurrence, fate and disposal, proceedings of a workshop held in Brussels on 26-27 October1988; 1989

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DEPARTMENT OF ENVIRONMENTAL SCIENCE AND ENGINEERING; Technical universityof Denmark; Uptake of toxic organics in plants and animals; in: management and fate of toxicorganics in sludge applied to land. Proceedings of the conference of Copenhagen; 1997

DIERCXENS P. HW�DO�; Apport par les boues de composés traces organiques dans les sols et lescultures; Gaz, eaux, eaux usées, 67(3), 123-132, 1987

DIGNAC (7�$/�, Fate of wastewater organic pollution during activated sludge treatment: nature ofresidual organic matter, Wat. res. 34(17) pp. 4185-4194, 2000

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DIRKZWAGER A. H. HW� DO�, Production, treatment and disposal of sewage sludge in theNetherlands, European Water Pollution Control, 7(2), 29-411, 1997

DOR F.; Impacts des rejets atmosphériques des incinérations de déchets ménagers et assimilés;1998

DOUBEN HW�DO�; Congener specific transfer of PCDD/Fs from air to cow's milk: an evaluation ofcurrent modelling approaches; Environmental pollution 95(3) 333-344; 1997

DOWDY HW�DO�; Trace metal movement in an aeric Ochraqualf following 14 years of annual sludgeapplication, J. Environ. Qual. 20:119-123; 1991

DOWDY, PAGE AND CHANG; Management of agricultural land receiving Wastewater sludge inSoil management for sustainability; 1991

DUARTE-DAVIDSON R., WILSON S.C., ALCOCK R.E., JONES K.C., Identification of priorityorganic contaminants in sewage sludge, volume 1, UK Water Industry Research Limited, 1995

DUCROT HW� DO�; Risque sanitaire toxicologique lié à l'épandage agricole des boues de stationd'épuration, revue méd. vét. 147(6) 439-444; 1996

EDMONDS; Survival of coliform bacteria in sewage sludge applied to a forest clearcut andpotential movement into groundwater; Applied Environmental Microbiology 32; 537-546; 1976

EFROYMSON R.A., MURPHY D.L., Ecological risk assessment of multimedia hazardous airpollutants: estimating exposure and effects, The Science of the total environment, 274, 219-230,2001

ELJARRAT HW�DO�; Decline in PCDD and PCDF levels in sewage sludges from Catalonia (Spain);Environmental science and technology 33(15) pp. 2493-2498, 1999

ELJARRAT HW�DO�; Effects of sewage sludge contaminated with polychlorinated dibenzo-p-dioxins,dibenzofurans, and biphenyls on agricultural soils; Environmental Science and Technology,31(10), 2765-2771, 1997

EMMERICH HW� DO.; Movement of heavy metals in sewage sludge-treated soils, Journal ofenvironmental quality 11, 174-178; 1982

FINNVEDEN HW� DO�; Solid waste treatment within the framework of life-cycle assessment. J.Cleaner. Prod. 3 (4) pp. 189-199; 1996

FRIES G. F.; Potential polychlorinated biphenyl residues in animal products from application ofcontaminated sewage sludge to land, J. environ. Qual. 11(1) 14-20; 1982

FROST H.L. and KETCHUM L.H.; Trace metal concentration in durum wheat from application ofsewage sludge and commercial fertiliser, Advances in environmental research, 4(4), pp. 347-355, 2000

GERRITSE HW� DO., Effect of sewage sludge on trace element mobility in soil, Journal ofEnvironmental Quality 11, 359-364; 1982

GILLER HW� DO�; Toxicity of heavy metals to micro-organisms and microbial processes inagricultural soils - a review; Soil Biology & Biochemistry 30, 1389-1414; 1998

GLANTZ and JACKS; Significance of (VFKHULFKLD�FROL serotypes in waste water effluent; Journalof the Water pollution control Federation 39, 1918-1921; 1967

GOMEZ HW� DO�; Définition des seuils de phytotoxicité de différents métaux susceptibles d’êtrerencontrés dans les boues de station d’épuration pour des sols à très faible teneur ou à très fortpouvoir de fixation vis-à-vis des cations; conv. Min. envir./ C.E.N. Cadarache/ INRA n° 79-81,108 p. ; 1982

GRIDEC; Evaluation des nuisances et impacts liés à l'incinération d'ordures ménagères etassimilés; 1996

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HAGENMAIER, H.; Untersuchungen der Gehalte an polychlorierten Dibenzodioxinen,polychlorierten Dibenzofuranen und ausgewählten Chlorkohlenwasserstoffen inKlärschlämmen; 1988

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HOLM HW�DO�; Measured soil water concentrations of cadmium and zinc in plant pots and estimatedleaching outflows from contaminated soils, Water, air and soil pollution 102: 105-115; 1998

HUYLEBROEK; Review of research projects on ground-water pollution from agricultural use ofsewage sludge. Treatment and use of Sewage sludge. Commission of the EuropeanCommunities, Cost Project 68 Bis, Final Report III, Technical Annexes, 491-521, 1981

JACKSON AND EDULJEE; An assessment of the risks associated with PCDDs and PCDFsfollowing the application of sewage sludge to agricultural land in the UK, Chemosphere 29(12)pp. 2523-2543; 1994

JACOBS HW� DO�; Effects of trace organics in sewage sludges on soil-plant systems and assessingtheir risk to humans, in Land application of sludge, proceedings of a workshop; 1989

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JAKSON AND ALLOWAY; The transfer of cadmium from sewage sludge amended soil into theedible components of food crops; Water, Air and Soil Pollution 57-58: 873-881; 1991

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JONES HW� DO�; Measured and predicted volatilisation fluxes of PCBs from contaminated sludge-amended soils; Environmental pollution 97(3) 229-238; 1997

JONES HW� DO�; Organic chemicals in contaminated land: analysis, significance and researchpriorities; Land contamination and reclamation 4(3) 189-197; 1996

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KAMPE; Cd and Pb in the consumption of foodstuffs depending on various contents of heavymetals; in L’Hermitte, and Ott, Processing and Use of sewage sludge, Reidel Publishingcompany Dordrecht; 334-348, 1984

KENRICK HW�DO.; Trace organics in British aquifers; Technical report TR 223, WRc Medmenham,Marlow; 1985

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KJELDSEN et CHRISTOPHERSEN, Composition of leachate from old landfills in Denmark,submitted for publication, 2000

KLADIVKO AND NELSON; Surface runoff from sludge amended soils, Journal of the waterpollution control federation; 51; 100-110; 1979

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KROGMANN HW�DO�; Biosolids and sludge management, Water environment research; 1999

KROGMANN HW�DO�; Biosolids and sludge management, Water environment research; 1998

KROGMANN HW� DO�; Biosolids and sludge management, Water environment research 69(4) pp.534-550; 1997

KRUSE AND BARRETT; Effects of municipal sludge and fertilizer on heavy metal accumulationin earthworms; environmental pollution (Series A) 38, 235-244; 1985

LAGRIFFOUL HW�DO�, Cadmium toxicity effects on growth, mineral and chlorophyll contents, andactivities of stress related enzymes in young maize plants (Zea mays L.), Plant and Soil 200, pp.241-250, 1998

LARKIN HW�DO�; Persistence of virus on sewage irrigated vegetables; Journal of the environmentalengineering division of the American Society of Civil Engineers; 102; 29-35; 1976

LISK D.J, BOYD R.D, TELFORD J.N, BABISH J.G, STOEWSAND G.S, BACHE C.A,GUTENMANN W.H.; Toxicologic studies with swine fed corn grown on municipal sewagesludge-amended soil; Journal of Animal Science, vol. 55, n°3, pages 613-618, 1982.

LUE-HING HW�DO.; Viral and bacterial levels resulting from land application of digested sludge; inSopper HW�DO� Utilization of municipal sewage effluent and sludge on forest and disturbed land,The pensylvania State University Press, pp. 445-462; 1979

MAGNUSSON AND HÅNEL; Pelleted Municipal Sludge – A Key Element in Future ResourceCycling and Sustainable Forest Management, presented at th XXI IUFRO World Congress, 7-12 August, Kuala Lumpur; 2000

MARANI HW�DO�, Partitioning of heavy metals in sewage sludge incineration, Annali di Chimica 88,pp. 887-899, 1998

MBILA HW�DO�; Pedogenesis of heavy metals polluted soils; non published thesis, 2000.

MCBRIDE M.; rowing food crops on sludge-amended soils: problems with the U.S. environmentalprotection agency method of estimating toxic metal transfer; Environmental toxicology andchemistry 17(11); 2274-2281; 1998

MCBRIDE M.; Toxic metal accumulation from agricultural use of sludge: are USEPA regulationsprotective?; Journal of environment quality 24(1) 5-17; 1995

MCBRIDE M.; Toxic metal accumulation from agricultural use of sludge: are USEPA regulationsprotective; Journal environment quality 24; 5-18; 1995

MCGRATH; Persistent organic pollutants and metals from sewage sludge: their effects on soil,plants and the foodchain, in: Workshop on problems around sludge, proceedings, Langenkamp,Marmo eds; 2000

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MCGRATH HW�DO�; Long-term effects of metals in sewage sludge on soils, micro-organisms andplants; Journal of industrial microbiology 14, 94-104; 1995

MCGRATH and LANE; An explanation for the apparent losses of metals in a long-term fieldexperiment with sewage sludge; environmental pollution 60, 235-256; 1989

MCGRATH, BROOKES and GILLER; Effects of potentially toxic metals in soil derived from pastapplications of sewage sludge on nitrogen fixation by 7ULIROLXP� UHSHQV L.; Soil Biology andBiochemistry 20, 415-424; 1988

MCGRATH S.P.; Long term studies of metal transfers following application of sewage sludge inPollutant transport and fate in ecosystems; Blackwell Scientific publication, pages 301-317,1987.

MCLACHLAN AND RICHTER; Uptake and transfer of PCDD/Fs by cattle fed naturallyContaminated feedstuffs and feed contaminated as a result of sewage sludge application 1.Lactating cows, J. Agric. Food Chem. 46(3) 1166-1172; 1998

MCLACHLAN HW�DO�; Persistence of PCDD/Fs in a Sludge-amended soil; Environmental science &technology 30(8) 2567-2571; 1996

MCLACHLAN HW� DO�; Polychlorinated dibenzo-p-dioxins and dibenzofurans in sewage sludge:sources and fate following sludge application to land, The science of the total environment185:109-123; 1996

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MICHELIN HW�DO�, Evaluation de l’état de contamination d’un sol agricole par les éléments tracesmétalliques lié à des apports réguliers de boues résiduaires urbaines depuis 1985, in press, 2001

MIEURE HW�DO�; Terrestrial safety assessment of linear alkylbenzene sulfonate, chemosphere 21(1-2) 251-262; 1990

MININNI HW�DO�, Partitioning of Cr, CU, Pb and Zn in sewage sludge incineration by rotary kiln andfluidized bed furnaces, Water research and technology, 41(8) pp. 61-68, 2000

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NILSSON C., Swedish environmental protection agency; Organic pollutants in sewage sludge,contribution to human exposure to certain estrogen-perturbing compounds; 1996

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O’CONNOR HW� DO�; Bioavailability to plants of sludge-borne toxic organics; Review ofenvironmental contamination and toxicology, 121, 129-155; 1991

ÖMAN HW�DO�; Transport fate of organic compounds with water through landfills, Wat res. 33(10)pp. 2247-2254; 1999

PAHREN HW�DO�; Health risks associated with land application of municipal sludge, journal WPCF51(11); 1979

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PERROTEY S.; Impacts écotoxicologiques et toxicologiques des métaux lourds; ADEME; 1993

PETIT K.; ENVA; Etude bibliographique sur la résistance des parasites aux traitements des bouesde stations d'épuration. Impact sur la santé publique. Thèse de doctorat vétérinaire; 1996

PIEPER HW� DO�; Determination of PCDD/F for hazard assessment in a municipal landfillcontaminated with industrial sewage sludge. Chemosphore 34 (1) pp 121-129; 1997

POHL & al.; Public health assessment for dioxins exposure from soil. Chemosphere 31 (1) pp.2437-2454; 1995

PRADEL J.P.; Utilisation agricole des boues des stations d’épuration des eaux usées, des compostsde déchets ménagers et de déchets verts dans le département du Val d’Oise; ENITA Bordeaux,1997.

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SAUERBECK D. and STYPERECK P., Schwermetallakkumulation durchKlärschlammanwendung - Ergebnisse aus 25 langjährigen Feldversuchen, VDLUFA –Schriftenreihe, 23, Kongreßband 1987

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SCRIMSHIRE, personal communication

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SIDHU HW�DO�; Hazardous air pollutants formation from reactions of raw meal organics in sementkilns; Chemosphere, 42, 499-506, 2001

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SMITH S.R.; Are controls on organic contaminants necessary to protect the environment whensewage sludge is used in agriculture; 1999

SMITH S.R.; Long-term effect of Zinc, Copper, and Nickel in sewage sludge-treated agriculturalsoil, proceedings of the 4th International Conference on the bioavailability of trace elements,June 23-26 1997, pp. 691-692

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TRASSAERT AND PEUCHOT; ADEME-IFTS; Bilan et perspectives de développement desmatériels de séparation liquide solide en déshydratation des boues résiduaires urbaines etindustrielles; 1995

TSAGARAKIS K.; HORAN N.; MARA D.; ANGELAKIS A.; Management of solids frommunicipal wastewater treatment plants in Greece, 4th European Biosolids and Organic ResidualsConference, Wakefield, 15-17/11/99 Paper No 35

VIGERUST and SELMER-OLSEN; Basis for metal limits relevant relevant to sludge utilisation; inDavis HW� DO�; Factors influencing sludge utilisation practices in Europe, Elsevier AppliedSciences Publishers Ltd, Barking, pp. 26-42; 1986

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WANG M.J., MCGRATH S.P. JONES K.C.; Chlorobenzenes in field soil with a history ofmultiple sewage sludge applications, Environmental science and technology 29, 356-362; 1995

WELCH and LUND; Soil properties, irrigation water quality and soil moisture level influences onthe movement of nickel in sewage sludge-treated soils, journal of environmental quality 16,403-410; 1987

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WERTHER J., OGADA T., PHILIPPEK C., CO- und NOx-Emissionen bei der Verbrennung vonKommunalen Klärschlämmen in der Wirbelschicht, Chem.-Ing.-Tech. 66 (10) pp. 1361-1364,1994

WHITWHAM M., Les pailles de céréales, évaluation du potentiel de pailles mobilisables à des finsénergétiques, Les cahiers du CLIP n° 10, september 1999

WIART, J., REVEILLERE, M.; La teneur en éléments traces métalliques des boues des stationsd'épuration urbaines françaises, TSM n° 12, Déc. 1995

WILD et JONES; Organic chemicals in the environment, Polynuclear aromatic hydrocarbon uptakeby carrots grown in sludge amended soil, J. Environ. Qual. 21:217-225; 1992

WILD HW� DO�; Polynuclear aromatic hydrocarbons in crops from long-term field experimentsamended with sewage sludge, Environmental pollution 76, 25-32; 1992

WILD HW�DO�; The influence of sewage sludge applications to agricultural land on human exposureto polychlorinated PCDDs and PCDFs, Environmental pollution 83 357-369; 1994

WILD HW�DO�; The polynuclear aromatic hydrocarbon (PAH) content of archived sewage sludges,Chemosphere 20(6) 703-716; 1990

WILLIAMS HW�DO�� Metal movement in sludge amended soils: A nine-year study, Soil Science 143,124-131, 1987

WILSON HW� DO�; Persistence of organic contaminants in sewage sludge-amended soil: a fieldexperiment; Journal of environmental quality 26(6) 1467-1477; 1997

WILSON HW� DO�; Volatile organic compounds in digested United Kingdom sewage sludges;Environmental Science and Technology 28, 259-266; 1994

WITTER HW�DO.; A study of the structure and metal tolerance of the soil microbial community sixyears after cessation of sewage sludge application; Environmental Toxicology and chemistry,19(8), 1983-1991, 2000

WITTER; Limit values for heavy metal concentrations in sewage sludge and soil that protect soilmicro-organisms, in: Workshop on problems around sludge, Proceedings, Langenkamp andMarmo eds; 2000

WITTER HW�DO�; Where's the limit? Changes in the microbiological properties of agricultural soils atlow levels of metal contamination; Soil Biol. Biochem. 29(9) 1405-1415; 1997

WITTER; Heavy metal concentrations in agricultural soils critical to micro-organisms, Swedishenvironmental protection agency, report 4079; 1992

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ZHAO F.J., DUNHAM S.J., MCGRATH S.P.; Lessons to be learned about soil-plant metaltransfers from the 50 years sewage sludge experiment at Woburn, UK, in: Extended abstracts of4th International Conference on the Biogeochemistry of Trace Elements June, 23-26 1997

ZMIROU D.; Traitement des déchets et risques sanitaires pour les riverains: évidences etincertitudes. Colloque ADEME, Recherche, Santé, Déchets: quelles priorités?; 1996

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Member States

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European Commission; 2000; Report from the Commission to the Council and the EuropeanParliament on the implementation of community waste legislation for the period 1995 – 1997;COM(1999)752

ADEME Arthur Andersen; 1999; Situation du recyclage agricole des boues d’épuration urbaines enEurope et dans divers autres pays du monde

AEA Technology plc; 1999; Compilation of EU dioxin exposure and health data

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For Denmark: Answer to the questionnaire

For Finland: Puolanne; Production and disposal of sewage sludge in Finland; National Board ofwaters and the environment; 1992

For Germany: Leschber; Organic pollutants in German Sewage Sludges and Standardization ofRespective Parameters; Deutsches Institut für Normung 1996

For Ireland: McGrath, 1996, Utilisation of sewage sludge in agriculture, future perspectives

For Italy: Answer to the questionnaire

For Netherlands: Dirzwager HW� DO�, Production, treatment and disposal of sewage sludge in theNetherlands, in Europ. Wat. Poll. Control 7(2)

For Portugal: Sequeira and Domingues 1993 in Marecos do Monte 1997

For Sweden: Statistics Sweden 1998 and Nilsson C.; Organic Pollutants in Sewage Sludge; 1996

For United Kingdom: CIWEM; Handbooks of UK wastewater practice; 1995

Accession Countries

The presented data originates from the questionnaires sent for the purpose of this study

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'DWH��IRU�PHWDOV� 1997 1997 1995 1997 1997 1997 1993 1997 1997 1993 1997 1998 1996

1��PJ�NJ�'0� 20 - 80 000 - 43 000 32 000 40 000 34 833 - 27 558 - 30 300 1 200 - 43 800 38 112 43 395

3��PJ�NJ�'0� 30 - 90 000 - 31 000 28 000 45 000 20 750 - 10 386 - 45 700 (P205) 300 - 39 000 27 702 22 394

.��PJ�NJ'0� - - 2 800 - - - - - - - - - - - -

PJ�NJ'0

&G 20 - 40 0.5 - 2 3 2.33 1.04 2.9 1.4 - 2.8 1.18 3.8 0.4 2.3 2 1.2 3.3

&U 1000 - 1750 40 - 275 75 38.0 84 58.8 46 - 165 75 51 16 72 204 35.7 157

&X 1000 - 1750 100 - 500 156 262 290 309 274 - 641 317 206 39 289 301 394.1 568

+J 16 - 25 0.3 - 2 1.1 1.33 1.3 3 1 - 0.6 0,78 1.9 0.5 - 1 1.1 2.4

1L 300 - 400 20 - 80 32 24.0 34 31.9 23 - 54 90 24 9 66 46 18.2 57

3E 750 - 1200 40 - 130 154 78.8 39 106.7 63 - 150 79 128 13 200 200 35.4 221

=Q 2500 - 4000 450 - 2 000 938 748 606 754.2 809 - 562 1010 1628 143 1 555 911 545.4 792

PJ�NJ'0

3$+ - - 1.8 0,018 - 11,9 - 0,1 - 0,6 - - - - 9.7 - - 1.8 1 - 10

3&% - - <0.005 - 0.140 0,038 – 0,243 - 0,01 - 0,04 - 0,067 - - 0.08 - - 0.1 0,01 - 213&''�)��QJ�7(��NJ�'0� 8,1 - 38 - 0,7 - 55 0,006 - 0,018 - 15 - 45 - - - - - - 64 0,02 - 115 9 - 192(2; - - - 5 - 226 - - - - - - - - - - -

$2; - - <0.02 - - 140 - 280 - - - - - - - - -

/$6� - - 374 - - - - - - - - - - - -

13( - - 8.1 - - - - - - - - - - 22.8 -

'(+3 - - 24.0 23 - 270 - 20 - 60 - - - - - - - 25 - 660 -

QE�J�ZP

6DOPRQHOOD - - 32 000 - - - - - - - - - - - -

(QWHULF�YLUXV - - - - - - - - - - - - - - -

&ROLIRUP - - 160 000 - - - - - - - - - - - -

(�FROL - - - - - - - - - - - - - - -

9LDEOH�+HOPLQWK�HJJV - - - - - - - - - - - - - - �

6WUHSWRFRFFL - - 3870 - - - - - - - - - - - -

(QWHURFRFFL - - - - - - - - - - - - - - -

1 See Further information concerning LAS in appendix 3

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(VWRQLD +XQJDU\ /DWYLD /LWKXDQLD 0DOWD 3RODQG 5RPDQLD 6ORYDNLD 6ORYHQLD

'DWH 1995 - 1999 1997/99 1990 - 1993 1999'U\�PDWWHU���� 22-73 12-45 37 15 - 14,1 1-352UJDQLF�0DWWHU����'0� 67-72 51.96 43 51 37,5 56,2 57.31���'0 3,75 - 4,53 3.52 1.09 3.5 67,02 mg/kg DM 4,6 3.43���'0 1,97 – 2,27 1.65 1.1 1.7 1454 mg/kg DM 0,9 2.2.���'0 0,25 – 0,26 0.35 - 0.16 610,4 mg/kg DM 0,3 0.17PJ�NJ'0&G 20 - 40 1,85 – 3,5 2.7 - 7.5 11,78 4,5 2.5&U 1000 - 1750 22 - 133 197.4 38.9 168 694,94 98,0 239&X 1000 - 1750 129 - 202 239.8 418.1 290 348,65 290 587+J 16 - 25 0,4 3.44 0.92 3.1 - 4,2 2.71L 300 - 400 30 - 32 39.9 75.3 65 143,73 38 1413E 750 - 1200 44 - 70 113.7 79.7 109 123,75 148 112=Q 2500 - 4000 659 - 1173 1450 592.6 1654 874,2 1680 1 452&R - - 9.1 - 12,53 - -$V - 12.5 - - - 7,7 -0R - 3.6 - - 4,29 3,2 -0Q - - 389.4 - - - -PJ�NJ'03$+ - - - 3.5 - 1,8 -3&% - 0.23 - 0.09 - 0,07 -3&''�) - - - - - - -$2; - 296 - - - 320 -/$6 - - - - - - -13( - - - 22 - - -'(+3 - - - - - - -QE�J�ZP6DOPRQHOOD - - - - - - -(QWHULF�YLUXV 4,3.104/100g - - - - - -&ROLIRUP - - - - - - -(�FROL - - - - - - -9LDEOH�+HOPLQWK�HJJV 0 - - - - - -6WUHSWRFRFFL - - - - - - -(QWHURFRFFL - - - - - - -

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3URSHUWLHV�DQG�PDLQ�FKDUDFWHULVWLFV

Lead is largely used in the industry for pipes, battery, and ammunition production. It is alsoincorporated to paintings. Its use in petrol is being reduced.

2ULJLQ�LQ�VOXGJH

There are two main origins for lead in sludge: water from road runoff and alteration of old pipes.Industrial effluents may also contain lead. Their contribution to the sludge content is of about 20 %.

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Origin of lead in soil is described in the following figure [Juste 1990]. It appears that most of thelead found in soil originates from atmospheric deposition.

12%

19%

1%68%

Agricultural wastes

Sludges

Fertilizers

Atmospheric fallouts

Figure 1: Origin of lead in soil [Juste, 1990]

According to the country, lead average level in European soils ranges between 10,5 and 35 mg/kgDM in sandy soils, and between 12 and 36 mg/kg DM in clay soils. [European Commission, JointResearch Center].

Lead is one of the OHDVW�PRELOH metal in soil. Lead is considered to be 100 times less mobile thanCadmium given identical total molar concentrations of the two metals and pH levels within therange of 5 to 9.

Lead’s ELRDYDLODELOLW\ in the soil is ORZ�and is only little influenced by soil pH. Lime treatment ofsludge would therefore not affect this property. Phosphates and sulphates, however, act aseffective immobilisation agents and can form complexes with lead.

&OD\�and in particular RUJDQLF�PDWWHU constitute the predominant absorption substratum; on thecontrary, contribution of iron and manganese oxides to lead retention is discussed.

The great affinity of Pb to organic matter explains its preferential accumulation in the soil’ssurface horizon. It is also cause of a higher sensitive to soil erosion, which would need furtherdocumentation.

8SWDNH�E\�SODQWV

Bioavailability of lead in soil is low. Plant absorption is therefore also low. Moreover, eventuallead absorption by plant leads to rapid immobilisation.

Even in rural areas, 90 to 99% of lead in the above ground parts of the plant is of DWPRVSKHULFRULJLQ. Lead is certainly one of the metals least readily transferred to the upper parts of the plant. It

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has been reported that lead concentration in plants grown on soil containing several hundreds ofmg/kg of total Pb rarely exceeded 30 to 50 mg/kg DM.

Field studies also shown that there is little accumulation of lead in crops.

Lead’s specific SK\WR[LFLW\ is certainly one of WKH�ORZHVW of all the metal micropollutants.

(FRWR[LFRORJ\

The Danish EPA [1997] summarised data concerning the Effect and No-Effect concentrations oflead on terrestrial organisms and plants. The results are presented below. It must be stressed thatthe results refer to studies performed under different conditions and protocols: various different soiltypes, organisms and duration are taken into account, the effects studied (mineralisation,nitrification, growth, mortality etc.) are different and the impact level on the population may varyaccording to the experiment. It is therefore recommended to refer to the publication of the DanishEPA.

2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

Microorganisms 10 – 7 500 10 – 6 860

Plants 10 – 1 000 25 – 5 000

Invertebrates 25 - > 15 996 50 – 10 830

7UDQVIHU�WR�KXPDQV�DQG�DQLPDOV

It seems that only 5 to 10% of lead ingested via drinking water or foodstuffs is assimilated and, upto 90% of which are stored in the skeleton. It transfers then slowly into the blood. Principalexcretion route is urine. Its half-life in blood is of about 20 – 30 days. Half-life in bones is about10 to 20 years [Sfsp 1999].

Lead generates anaemia and renal disturbance. When exposed to high levels (1 200 µg/l in blood),paralysis of upper members and encephalopathy have been observed. Children exposed presentslower brain development. The long-lasting absorption of lead leading to lead in blood of 400 µg/lconducts to chronic intoxication. As a consequence, children may suffer from psychomotor andintellectual disturbances, and adults from hypofertility.

The WROHUDEOH�ZHHNO\ H[SRVXUH�KDV�EHHQ�VHW�DW���� J�NJ�RI�ERG\�ZHLJKW�LQ������>)$2�DQG�:+2@�A draft Commission regulation proposes to set maximum levels for some heavy metals in foodstuffas described in the following table2. It must be stressed that those limit values have been set basedupon what is achievable using good working practice. The Scientific Committee for Food howeverrecommended that those values should be as low as reasonably achievable.

2 Draft Commission regulation setting maximum levels for certain contaminants in foodstuff amending

commission regulation EC n° 194/97 of 31 January 1997. ENTR/5799/99 – rev 1 - EN

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1. Cow’s milk (liquid, as consumed) 0,02 mg/l

2. Meat of cattle, sheep and pig, poultry meat (except game) 0,05 mg/kg

2.1. Edible offal of cattle, pig and poultry 0,5 mg/kg

3. Fish 0,2 mg/kg

4. Crustaceans 1,0 mg/kg

5. Bivalve molluscs 2,0 mg/kg

6. Cereals, leguminous and pulses, excluding bran and germ 0,2 mg/kg

7. Vegetables, excluding brassica, leafy vegetables, mushrooms and potatoes 0,1 mg/kg- 7.1 Brassica, leafy vegetables and mushrooms- 7.2 Potatoes

0,3 mg/kg0,15 mg/kg

8. Fruits (as consumed) 0,1 mg/kg

9. Fats and oils, including milk fat 0,1 mg/kg

10. Fruits juices 0,05 mg/l

11. Wines, including liqueur wines, sparkling wines, ciders, perry and fruit wines 0,1 mg/l

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Zinc is used in surface treatment and is mostly used in alloys. It is also found in battery, asprotective layer in the building industry, in textile, pharmaceutical and insecticide industry.

2ULJLQ�LQ�VOXGJH

Zinc originates mostly from pipe alteration, and in a secondary extent, from industrial effluents.

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Origin of zinc in soil is described in the following figure [Juste 1990]. It appears that most of thezinc found in soil originates from agricultural wastes spread on land.

61%20%

1%

18%

Agricultural wastes

Sludges

Fertilizers

Atmospheric fallouts

Figure 2: origin of Zinc in soil [Juste, 1990]

According to the country, zinc average level in European soils ranges between 18 and 106 mg/kgDM in sandy soils, and between 35 and 76 mg/kg DM in clay soils. [European Commission, JointResearch Center].

The most common and mobile form of Zn is Zn2+ although other ionic forms may exist in soil.Clays, Fe and Al hydroxides as well as organic matter may strongly bind this metal.

Zn is considered as PRUH�VROXEOH than other trace metals in soil. It becomes highly DYDLODEOH�andYHU\�PRELOH�LQ DFLGLF�VRLOV�

8SWDNH�E\�SODQWV

Zn can be absorbed by many plant species. Roots often contain more Zn than the above groundparts of the plant. However Zn bound to small organic compounds is transported within the plantvia the xylem.

=LQF¶V� HVVHQWLDO� IXQFWLRQV within the plants are linked to the metabolism of sugars, proteins,phosphate, auxins3 and nucleic acids. Zn also affects plant’s resistance to stresses caused bydrought or pathogenic agents.

3 Plant hormone regulating growth, particularly cell elongation

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The WKUHVKROG�IRU�GHILFLHQF\ has been assessed to be around 10 to 20 mg/kg of dry matter but thevalues vary according to the interactions between Zn and the other elements in the plants.3K\WRWR[LFLW\ can be considered as occurring at zinc levels in the plant in excess of 100 to 400mg/kg of dry matter.

Most plants show VLJQLILFDQW�WROHUDQFH�WR�H[FHVVLYH�OHYHOV of Zn. Beet and spinach are the mostsensitive. The symptoms are chlorosis, retarded plant growth and modifications to the roots.

Cd, Cu and Fe are the metals that compete most strongly with zinc for absorption and transfer.Generally, there is antagonism but, depending on the Cd/Zn ratio there can be synergetic effects.

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The Danish EPA [1997] summarised data concerning the Effect and No-Effect concentrations ofzinc on terrestrial organisms and plants. The results are presented below. It must be stressed thatthe results refer to studies performed under different conditions and protocols: various different soiltypes, organisms and duration are taken into account, the effects studied (mineralisation,nitrification, growth, mortality etc.) are different and the impact level on the population may varyaccording to the experiment. It is therefore recommended to refer to the publication of the DanishEPA.

2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

Microorganisms 2.5 – 1000 4.6 – 1000

Plants 0.35 – 50 1.8 – 250

Invertebrates 10 – 326 10 – 1000

7UDQVIHU�WR�KXPDQ�DQG�DQLPDOV

=LQF� LV� HVVHQWLDO in animal kingdom for many physiological processes: growth and cellulardifferentiation, reproductive functions and embryo development, the integrity of the skin andhealing, the immune system, the development and functioning of the nervous system and thesensory system. Zinc is also involved in gene expression.

Maximum tolerable dietary levels for animals have been assessed to be about 500 mg/kg DM[Smith 1996]. Any evaluation of the dangers associated with zinc must take into account the twofollowing points:

- Zinc’s ELR�DYDLODELOLW\� GHSHQGV� RQ� HQGRJHQRXV� IDFWRUV (metabolism, homeostasis) andH[RJHQRXV�IDFWRUV (the effects of proteins, food fibre),

- Zinc LQWHUDFWV�ZLWK�PHWDOV: zinc reduces the bioavailability of copper and protects against thetoxic effects of cadmium and nickel [Martin, 1996].

=LQF�LV�IL[HG�LQ�WKH�ERQHV��OLYHU�DQG�NLGQH\V.

0HDW�DQG�FHUHDO products are the food categories that contribute most to the human intake of zinc,providing respectively 41% and 21% of total contribution [Hercberg, 1991; Lalau et Al, 1996].

The average daily intake in France is estimated as being between 8,5 to 11,7 mg per day [Maland,1994]. The recommended nutritional amount of zinc is 15 mg per day for human beings [Bupin,1992].

The average contribution from food only covers 60 to 70% of the nutritional level in zinc.

$Q� LQFUHDVH� LQ� ]LQF� OHYHOV� LQ� IRRG��ZKLOH� VWLOO� UHPDLQLQJ�ZLWKLQ� DFFHSWDEOH� WROHUDQFHV�� FRXOGSURYH�EHQHILFLDO�WR�KXPDQ�KHDOWK�

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Cadmium is a soft, ductile metal which is usually obtained as a by-product from the smelting oflead and zinc ores. The principal use of cadmium is as a constituent in alloys and in theelectroplating industry. Other uses of cadmium include paints and pottery pigments, corrosion-resistant coating of nails, screws, etc, in process engraving, in cadmium-nickel batteries, and asfungicides. Cadmium is also naturally present in soils and mineral fertilisers.

2ULJLQ�LQ�VOXGJH

Cadmium in sludge has mainly an industrial origin, but can also originate from householdeffluents: cadmium is present in cosmetic products and gardening pesticides. It also comes from therunoff of raining water, after atmospheric deposition of the metal.

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Origin of Cadmium in soil is described in the following figure.

20%

38%2%

40%

Agricultural wastesSludgesFertilizersAtmospheric fallouts

Figure 3: origin of cadmium in soil [Juste 1990]

According to the country, cadmium average level in European soils ranges between 0,1 and 1mg/kg DM in sandy soils, and between 0,2 and 0,3 mg/kg DM in clay soils. [EuropeanCommission, Joint Research Center].

Cadmium is relatively mobile compound in most soils. It is more mobile than zinc but less mobilethan nickel [Legret HW�DO, 1988]. Its mobility essentially depends on the pH; the metal’s adsorptionto the soil’s solid phase can be multiplied threefold for every unitary increase in pH in a range from4 to 8.

On land spread with sludge at Woburn (Great Britain), bacterium Rhizobium leguminosarumbiovar trifolii failed to fix any nitrogen because of the toxic effects of the heavy metals on itself. Inthe studied soils, cadmium levels were significantly higher than those of other heavy metals[Chaudri, 1992]. These high levels of cadmium would explain the lack of nitrogen fixation whenthe levels of other trace elements (particularly copper and zinc) are low.

Available data would suggest that cadmium in the soil at levels of around 3 mg/kg has no negativeeffect on symbiotic N2 fixation.

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Cd may be� DEVRUEHG by plants. The S+� level is one of the most important factors controllingcadmium absorption. Transfer factors are given in the main part of the report.

Compared with other micropollutants such as Cu or Pb, transfer of Cd to the above ground parts ofthe plant may be considered as significant. Concentration in roots represents only 2 to 5 times thatin the above ground parts but cadmium is transferred only with difficulty to reproductive or storageorgans of the plant.

The export of cadmium by crops must be considered as negligible, the percentage of metalexported in comparison to the amount present in the substratum never being greater than 1%.However, FDGPLXP�OHYHOV in the liver and kidneys increased DFFRUGLQJ�WR�WKH�GRVDJH�RI�VOXGJHapplied to the crops.

No deficiency level for cadmium is known. On the contrary, cadmium is well known as a KLJKO\SK\WRWR[LF element. Besides UHWDUGLQJ� JURZWK, phytotoxicity also occurs through FKORURVLV,which can be followed in the case of acute cadmium poisoning by QHFURVLV. Phytotoxicity levelsfor cadmium are given in the main part of this report.

Other compounds including Fe, Se, Mn and particularly Zn are antagonistic to Cd.

The growth of cadmium-resistant plants such as tomatoes and cabbages is only affected whencadmium concentration in soil reaches five to ten times levels that affect sensitive plants such assoya, spinach, lettuce and many leguminous plants.

7UDQVIHU�WR�DQLPDOV

Cadmium is particularly highly toxic to animals. Even a diet based on foodstuffs containing verylow levels of cadmium would cause growth deficiencies in rats and goats [Anke HW� DO�, 1984].Experimentally, cadmium also provoked cancers on some animal species.

Cadmium accumulates in the organism as its biological half-life is about 30 years.

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The Danish EPA [1997] summarised data concerning the Effect and No-Effect concentrations ofcadmium on terrestrial organisms and plants. The results are presented below. It must be stressedthat the results refer to studies performed under different conditions and protocols: various differentsoil types, organisms and duration are taken into account, the effects studied (mineralisation,nitrification, growth, mortality etc.) are different and the impact level on the population may varyaccording to the experiment. It is therefore recommended to refer to the publication of the DanishEPA.

2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

Microorganisms 1.5 – 1000 2.6 – 1000

Plants 0.35 – 50 1.8 – 250

Invertebrates 10 – 326 10 - 1000

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Highest cadmium concentrations are generally found in the renal cortex, and by increasingexposure levels, the metal may also be stored in the liver. Long term exposure to cadmium leads to

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renal dysfunction, and epidemiological studies carried out on exposed workers population showeda wide variety of effects, such as:

- Irritation of upper respiratory tract

- Metallic taste in the mouth

- Cough

- Chest pain

Cadmium and cadmium compounds have been classified as FDUFLQRJHQLF.

No dose-response function is available for non-carcinogenic effects. The Food and Agriculture2UJDQLVDWLRQ� �)$2�� LQGLFDWHV�PD[LPXP�GDLO\� H[SRVXUH� YDOXH� RI� ��� J� RI� FDGPLXP� SHU� GD\�� ,QFebruary 1993, the joint FAO/WHO Expert Committee on food additives agreed to maintain theprovisional tolerable weekly intake of cadmium at 7 µg/kg body weight.

9HJHWDEOHV� DQG� FHUHDOV contribute the most to the cadmium exposure, representing 60% of theWRWDO�H[SRVXUH��&XUUHQW�HVWLPDWHV�RI�FDGPLXP�LQWDNH�DUH�RQ�DYHUDJH���� J�SHU�SHUVRQ�SHU�GD\��L�H�around 33% of the tolerable weekly intake [Becloitre, 1998].

A draft Commission regulation proposes to set maximum levels for some heavy metals in foodstuffas described in the following table4. It must be stressed that those limit values have been set basedupon what is achievable using good working practice. The Scientific Committee for Food howeverrecommended that those values should be as low as reasonably achievable.

)RRGVWXII 0D[LPXP�OHYHO

1. Meat of cattle, lamb, pig and poultry 0,05 mg/kg

2. Meat of horse 0,2 mg/kg

3. Liver of cattle, lamb, pig horse and poultry 0,5 mg/kg

4. Kidney of cattle, lamb, pig, horse and poultry 1,0 mg/kg

5. Fish 0,05 mg/kg

6. Crustaceans, except crab 0,5 mg/kg

7. Molluscs and crab 1,0 mg/kg

8. Cereals, except wheat grain and rice 0,1 mg/kg8.1 Wheat grain and rice 0,2 mg/kg

9. Soybeans and peanuts 0,2 mg/kg

10. Vegetables and fruits, excluding leafy vegetables, root vegetables, mushroomsand potatoes

0,05 mg/kg

10.1 Leafy vegetables and mushrooms 0,2 mg/kg

10.2 Root vegetables and potatoes 0,1 mg/kg

4 Draft Commission regulation setting maximum levels for certain contaminants in foodstuff amending

commission regulation EC n° 194/97 of 31 January 1997. ENTR/5799/99 – rev 1 - EN

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Nickel is used for the production of stainless steel and in alloys for coins and different instrumentsproduction. It is also used for metal surface treatment and battery production.

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Nickel in sludge originates from household effluents (cosmetic products and pigments) but alsofrom industrial effluents from the activities mentioned above.

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According to the country, nickel average level in European soils ranges between 2,9 and 38,2mg/kg DM in sandy soils, and between 7,5 and 33,3 mg/kg DM in clay soils. [EuropeanCommission, Joint Research Center].

The KLJK� PRELOLW\� DQG� ELRDYDLODELOLW\ of nickel of H[RJHQRXV� RULJLQ (sludge, salts…) incomparison with other metals has frequently been observed. On the other hand, there isinsufficient information regarding the potential mobility of the nickel pre-existing in soil.

8SWDNH�E\�SODQWV

The majority of plants only DEVRUE Ni with GLIILFXOW\�� In the case of cereal crops, and particularlybarley and oats, Ni may be transferred to the grain at the moment of senescence. Transfer factorsare given in the main part of this report.

Co, Cu, Fe and Zn compete with nickel during its absorption and transfer.

Nickel’s SK\WRWR[LF�HIIHFWV are well known. In fact, Ni is classified, along with Cd, Co, Hg andT1, as one of the PRVW�WR[LF�metals. 1LFNHO�KRZHYHU�LV�DOVR�LPSRUWDQW�IRU�SODQWV and is involvedin the metabolism of nitrogen. Toxicity and deficiency levels are given in the report.

The production of biomass is rapidly affected. In non-accumulative plants it can be suspected thatphytotoxicity would occur at nickel levels in the plant in excess of 5 to 10 mg/kg of dry matter.

Palacios HW� DO� [1999] studied the specific impact of sewage sludge application on tomato fruityield and quality. It was reported that sewage sludge addition to the calcareous soil of theexperiment significantly increased fruit yield but did not adversely affect the quality and thenutritional status of the tomato fruit. Only the highest addition rate of Ni to the sludge amendedcalcareous soil (240 mg.kg-1) had negative effects on fruit yield and quality and caused a Niaccumulation in fruit which could be considered as an hazard for human health.

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1LFNHO� LV� HVVHQWLDO to the functioning of urease in animals and deficiency causes functionalproblems in the liver and disrupts iron nutrition.

&KURQLF�WR[LFLW\ often appears at the reproductive level. Its effects are linked with concentrationsof nickel in food about 250 mg/kg of dry matter or 5 mg/1 in drinking water. There is a risk ofchronic toxicity in cattle, sheep and pigs when their daily feed regularly contains more than 50mg/kg of nickel.

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The Danish EPA [1997] summarised data concerning the Effect and No-Effect concentrations ofnickel on terrestrial organisms and plants. The results are presented below. It must be stressed thatthe results refer to studies performed under different conditions and protocols: various different soiltypes, organisms and duration are taken into account, the effects studied (mineralisation,nitrification, growth, mortality etc.) are different and the impact level on the population may varyaccording to the experiment. It is therefore recommended to refer to the publication of the DanishEPA.

2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

Microorganisms 17 – 1470 10 – 1470

Plants 50 – 335 12.5 – 500

Invertebrates 50 – 85 37 – 2500

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1LFNHO�LQWDNH�KDV�EHHQ�HVWLPDWHG�WR�EHWZHHQ�����DQG����� J�GD\�ZLWK�����J�IRU�GULQNLQJ�ZDWHU�

Individual daily requirements are about 35 µg. Acute toxicity only occurs in adults followingabsorption of around 250 mg of the metal ingested in the form of soluble salts.

Nickel is not a metal that accumulates to any significant extent throughout the food chain.

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Major sources of copper are from the industry (copper industry, non-ferrous metals industry,incineration).

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Copper in sludge and wastewater comes mainly from household effluents (domestic products, pipescorrosion…) but can also have an industrial origin (surface treatments, chemical and electronicindustry).

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Origin of copper in soil is described in the following figure.

55%

28%

1%

16%

Agricultural wastesSludgesFertilizers

Atmospheric fallouts

Figure 4: origin of copper in soil [Juste, 1990]

According to the country, copper average level in European soils ranges between 5,6 and 23 mg/kgDM in sandy soils, and between 7,4 and 23,8 mg/kg DM in clay soils. [European Commission,Joint Research Center].

Metals fix themselves preferentially to the soil organic matter, iron and manganese oxides andclays. The distribution of copper between these three fractions depends on the soil’s pH level, thequantity and the composition of the organic matter. It tends to migrate very little.

8SWDNH�E\�SODQWV

Copper is essential to plant nutrition. It plays an important role in photosynthesis and respiration.Copper’s phytotoxic effects are retarded growth of the roots and the above ground parts, thickeningof the roots and chlorosis. Levels of toxicity, deficiency as well as transfer factors are given in themain part of this report.

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The largest proportion of the copper present in the roots is not transferred to the above groundparts. The transport to and localisation of the metal in the various organs are controlled by theplant’s nitrogen metabolism process.

The absorption of copper by plants depends on the soil’s pH, which controls the activity of theCopper ions contained in the soil solution. Zn, Ca, K and N have an antagonistic effect on suchabsorption.

A pH levels lower than 6, symptoms of phytotoxicity occur when the level of exchangeable Cuexceeds 25 mg/kg in sandy soils and 100 mg/kg in clay-laden soils [Bonneau and Souchier, 1979].

(FRWR[LFRORJ\

The Danish EPA [1997] summarised data concerning the Effect and No-Effect concentrations ofcopper on terrestrial organisms and plants. The results are presented below. It must be stressed thatthe results refer to studies performed under different conditions and protocols: various different soiltypes, organisms and duration are taken into account, the effects studied (mineralisation,nitrification, growth, mortality etc.) are different and the impact level on the population may varyaccording to the experiment. It is therefore recommended to refer to the publication of the DanishEPA.

2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

Microorganisms 10 – 1445 10 – 3323

Plants 20 – 400 15 – 1600

Invertebrates 13 – 2609 27 – 2609

7UDQVIHU�WR�DQLPDOV�DQG�KXPDQV

Copper is implied in many physiological functions including hematopoesis, elastin and collagensynthesis, and in oxydo-reduction reactions. Copper is also a co-enzyme in many metalo-proteins.It is an essential element, of low toxicity.

Copper is not considered as human carcinogenic.

Instead, pathological symptoms are more related to copper deficiency. However, more data isneeded in order to describe dose response functions.

The main sources of copper in human food are meat products (27% of total contribution), cereals(28%), fruit and vegetables (21%) and dairy products (13%).

Adult copper requirements vary between 1.5 to 3 mg per day [Food and Nutrition Board, 1989].

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Large amounts of chromium are found in terrestrial crust. The most important part of the extractedchromium is used in alloys, for instance to produce stainless steel. It is also used for its heatresistance and wood protection properties, and, in chemical industry, as tanning agent, andpigment. Chromium may be found in several forms, mainly trivalent (referred to as CrIII), orhexavalent (referred to as CrVI).

2ULJLQ�LQ�VOXGJH

According to the level of industrialisation of the region, the origin of chromium found in sludgecan be divided as follows:

- 35 to 50 % from industry (surface treatment, tannery, chemical oxidation),

- 9 to 50 % from runoff (dust, pesticide, fertilisers),

- 14 to 28 % from household effluent.

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SYPREA5 assessed the origin of chromium in soil. Results are summarised below:

2ULJLQ $PRXQW��J�KD�\HDU�

Sludge 120

Fertiliser 800 - 1000

Agricultural waste 40 - 60

According to the country, chromium average level in European soils ranges between 6,4 and 59mg/kg DM in sandy soils, and between 13,2 and 27,8 mg/kg DM in clay soils. [EuropeanCommission, Joint Research Center].

Chromium mobility in soil seems to be very low. Below 1% of the total Chromium in soil can beextracted using current reagents. It depends however on its form. Trivalent chromium is mainlybound to the soil particles, primarily to organic matter, clay or other negatively chargedcompounds, or it may precipitate as trivalent oxides. Hexavalent chromium is anionic, does notinteract with clay and organic matter and remains mobile in solution. In inorganic soils with highpH, added hexavalent chromium may persist for a long time, however, if organic matter is present,hexavalent chromium may be reduced to the trivalent form [Danish EPA 1995].

8SWDNH�E\�SODQWV

The essential nature of chromium with regard to plants is unknown, however it is a normalcomponent of plants. Cases of phytotoxicity due to chromium are rare and vary according to thespecies concerned. The symptoms are chlorosis occurring in the young leaves.

5 French professional organisation for organic waste supply to land

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Whatever its form, the metal concentrates essentially in the URRWV and is very little transferred to theupper parts of the plant (< 10% of the total).

Transfer factors are given in the main part of this report.

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The Danish EPA [1997] summarised data concerning the Effect and No-Effect concentrations ofchromium on terrestrial organisms and plants. The results are presented below. As Chromium IIIand VO do not present the same level of toxicity, values are given for the two different states. Itmust be stressed that the results refer to studies performed under different conditions and protocols:various different soil types, organisms, duration are taken into account, the effects studied(mineralisation, nitrification, growth, mortality etc.) are different, and the impact level on thepopulation may vary according to the experiment. It is therefore recommended to refer to thepublication of the Danish EPA.

2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

&KURPLXP�,,,

Microorganisms 50 – 260 5.3 – 1300

Plants 50 – 1360 50 – 5000

Invertebrates 32 – 320 155 – 1000

&KURPLXP�9,

Microorganisms 0.09 – 520 1 – 5.3

Plants 0.35 – 230 1.8 – 750

Invertebrates 2 10 – 15

7UDQVIHU�WR�DQLPDOV�DQG�KXPDQV

&KURPLXP�LV�HVVHQWLDO to human and animal nutrition as it is implied in the sugar metabolism.

The two different oxidation states do not present the same level of toxicity, the hexavalent formbeing more toxic. Hexavalent chromium, contrary to the trivalent form, easily crosses membranesand binds to cellular proteins. The toxic effect of the hexavalent form is to a large degree due to thestrong oxidizing effect of this ion [Danish EPA 1995]. It has been shown that chromium could haveJDVWUR�LQWHVWLQDO� HIIHFWV, as well as impacts on the nasal wall and mucous membranes. Onceabsorbed, chromium is very little assimilated (about 0,43% assimilation) and through mechanismsthat are little understood. &KURPLXP�9, has been classified as FDUFLQRJHQLF�to humans.

Deficiency symptoms may be observed when present at too low concentration in diet. Studies ofhuman nutrition have shown that our daily diet is RIWHQ�GHILFLHQW� LQ�&KURPLXP� Measurementscarried out on different diets in North America and Europe showed GDLO\�LQWDNHV varying from 20to 30 µg per day and lying slightly below what should be contained in a normal daily diet (50-200µg) [National Research Council, 1980].

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3URSHUWLHV�DQG�PDLQ�FKDUDFWHULVWLFV

Mercury exists under GLIIHUHQW�FKHPLFDO�IRUPV determining its WR[LFLW\ and ELRDYDLODELOLW\�

Under its LQRUJDQLF�IRUP, mercury is present in the air as dust or in water. It has a natural presencein the environment, but also originates partly from industrial activity: mining, founding, coalcombustion, incineration. Mercury can easily be found under its gaseous form.

Under RUJDQLF� IRUP, mercury is mainly present in alimentation as it results from a biologicalprocess and therefore concentrates in the food chain.

2ULJLQ�LQ�VOXGJH

Mercury comes from pharmaceutical products, broken thermometers, runoff water, to whatindustrial discharge may be added.

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Navarre HW�DO� [1980] assessed the origin of mercury in soil. Results are summarised below.

2ULJLQ $PRXQW��PJ�KD�\HDU�

Atmospheric deposition 200

Fertilisers 245

Agricultural wastes 62

According to the country, mercury average level in European soils ranges between 0,03 and 0,05mg/kg DM in sandy soils, and between 0,04 and 0,08 mg/kg DM in clay soils. [EuropeanCommission, Joint Research Center].

In most soils, mercury is singularised by its essential ability to methylise through the actions ofaerobic or anaerobic bacteria or by simple chemical reaction with the fulvic acids produced byorganic matter.

The formation of these highly volatile organic compounds is the reason of VLJQLILFDQW� losses,representing some 30 to 60% of the mercury added to the soil, occurring in open field conditions.

Once added to the soil, mercury is also UDSLGO\� LPPRELOLVHG in the form of carbonates andphosphates fixed by iron, aluminium and manganese oxides and particularly by the organic matter,with which it forms highly stable organo-metallic compounds.

The S+� OHYHO does QRW appear to be D�GHWHUPLQLQJ� IDFWRU capable of affecting the PRELOLW\ ofmercury in the soil.

Because mercury is strongly bound to the solid phase, its concentration in the soil solution isSUDFWLFDOO\�XQGHWHFWDEOH. Mercury tends to remain in the soil’s VXUIDFH�KRUL]RQ.

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7UDQVIHU�WR�SODQWV

Plants grown on soils with current mercury concentrations rarely contain mercury levels exceeding50 µg kg-1 of dry matter.

Toxicity of mercury to plant depends on the speciation, affecting its penetration into livingorganisms.�The volatilisation of mercury in the soil and its absorption by the above ground parts ofplants can increase the level of mercury in plants [Lindberg et al, 1979].

The Biological Concentration Factors (BCF) (with dry matter reference) between pH 4 and 6 are0.02 for potato and 0.10 for cabbage [Sauerbeck and Stypereck, 1988]

In the case of cereals, +J�OHYHOV�UDQJH from 10 to 25 µg kg-1 of dry matter in the grain and from 25to 50 µg kg-1 of dry matter in the stalk.

95% of the mercury absorbed by plants accumulates in the URRWV. The effect of the soil’s S+�OHYHOon the metal’s ELRDYDLODELOLW\ is highly variable.

The metal found in the above ground parts of the plant essentially originates from mercuryabsorbed from the atmosphere through direct contact and absorption by the leaves’ stomata.

Mercury is also singularised by its significant ability to transfer from one plant organ to another.

2UJDQLF� RU� LQRUJDQLF� FRPSRXQGV of mercury DUH� WR[LF� WR� PRVW� SODQWV, with a phytotoxicitythreshold varying from 0.5 mg kg-1 of dry matter for rice to 3 mg kg-1 of dry matter for otherspecies, corresponding to a total concentration of mercury in the soil of around 50 mg kg-1.

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The Danish EPA [1997] summarised data concerning the Effect and No-Effect concentrations ofLQRUJDQLF mercury on terrestrial organisms and plants. The results are presented below. It must bestressed that the results refer to studies performed under different conditions and protocols: variousdifferent soil types, organisms and duration are taken into account, the effects studied(mineralisation, nitrification, growth, mortality etc.) are different and the impact level on thepopulation may vary according to the experiment. It is therefore recommended to refer to thepublication of the Danish EPA.

2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

Microorganisms 0.03 – 100 0.1 – 502

Plants 1 – 50 1 – 250

Invertebrates 0.121 – 1.21 0.121 – 6.05

7UDQVIHU�WR�DQLPDOV�DQG�KXPDQV

Under its metal form, PHUFXU\� LV� YRODWLOH and penetrates the body through inhalation, foodingestion and dental amalgam. Dermal exposure should also not be neglected. The half-life time ofmercury is about 70 days for methylmercury (MeHg), 40 days for Hg2+ and between 35 and 90days for Hg.

Metal mercury impacts on human health have mainly been observed on the nervous system.Symptoms are trembling (initially affecting hands) and emotional fragility [Sfsp 1999].Neuromuscular affections have also been observed. Other forms of non-organic mercury may alsoinduce renal dysfunction. Methylmercury has effects on nervous system, inducing developmentdelaying [Sfsp 1999].

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Methylmercury has been classified as possibly FDUFLQRJHQLF�according to studies carried out onanimals, but data available for humans does not allow concluding. Other forms of mercury have notbeen classified yet regarding their carcinogenicity.

Mercury levels in cereals, meat products, fruits and vegetables range from 6 to 20� J�NJ��'DLU\products and the soil strata contain only low amounts of mercury. )LVK is the SULPDU\�VRXUFH ofmercury in food.

In terms of human consumption, the WHO and FAO recommend a maximum daily intake of 43 µgper day for the total amount of mercury absorbed by an human adult and 29 µg per day in the caseof methyl-mercury.

A draft Commission regulation proposes to set maximum levels for some heavy metals in foodstuffas described in the following table6. It must be stressed that those limit values have been set basedupon what is achievable using good working practice. The Scientific Committee for Food howeverrecommended that those values should be as low as reasonably achievable.

)RRGVWXII 0D[LPXP�OHYHO

1. Fishery products, except those in 1.1 0,5 mg/kg

1.1 Anglerfish (Lophius spp.) 1,0 mg/kg

Atlantic catfish (Anarhichas lupus)

Bass (Dicentrarchus labrax)

Blue ling (Molva dipterygia)

Bonito (Sarda spp.)

Eel (Anguilla spp.)

Halibut (Hippoglossus hippoglossus)

Little tuna (Euthynnus spp.)

Marlin (Makaira spp.)

Pike (Esox lucius)

Plain bonito (Orcynopsis unicolor)

Portuguese dogfish (Centroscymnes coelopepis)

Rays (Raja spp.)

Redfish (Sebastes marinus, S. mentella)

Sailfish (Istiophorus platypterus)

Scabbard fish (Lepidopus caudatus, Aphanopus carbo)

Shark (all species)

Sturgeon (Acipenser spp.)

Swordfish (Xiphias gladius)

Tuna (Thunnus spp.)

6 Draft Commission regulation setting maximum levels for certain contaminants in foodstuff amending

commission regulation EC n° 194/97 of 31 January 1997. ENTR/5799/99 – rev 1 - EN

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6XPPDU\�RI�SURSHUWLHV��RFFXUUHQFH��IDWH�DQG�WUDQVIHU�RI�WKH�SULQFLSDO�RUJDQLF�FRQWDPLQDQW�JURXSV�IRXQG�LQ�VHZDJH�VOXGJH�DQG�VOXGJH�WUHDWHG�VRLOV�>6PLWK�����@

&RPSRXQG�JURXS 3K\VLFR�FKHPLFDO�SURSHUWLHV &RQFHQWUDWLRQ�LQ�VOXGJH 'HJUDGDWLRQ /HDFKLQJSRWHQWLDO

3ODQW�XSWDNH 7UDQVIHU�WR�DQLPDOV

3RO\QXOHDU�DURPDWLFK\GURFDUERQV��3$+V�

Water soluble/volatile to lipophilic 1-10 mg kg-1 Weeks Å 10 years Stronglyadsorbed by soil O.M.

None Very poorFoliar absorption

Possible but rapidly metabolisedNot accumulated

3KWKDODWH�DFLG�HVWHUV Generally lipophilic, hydrophobicand non-volatile

High1-100 mg kg-1

RapidHalf-life <50 days

None Root retentionNot translocated

Very limited

/LQHDU�DON\EHQ]HQH�VXOSKRQDWHV��/$6�

Lipophilic Very high50-15000 mg kg-1

Very rapid in aerobicenvironment

None None None

Alkylphenols Lipophilic 100-3000 mg kg-1 Rapid < 10 days None Minimal Minimal3RO\FKORULQDWHG�ELSKHQ\OV�3&%V�

Complex, > 200 congeners lowwater solubility, highly lipophilicand semi-volatile

1-20 mg kg-1 Very persistentHalf-life several yearsStrongly adsorbed by soil O.M.

None Root retentionFoliar absorptionMinimal root uptake andtranslocation

Possible into milk/tissues via soilingestionLong half-life

3RO\FKORULQDWHGGLEHQ]R�3�GLR[LQV�DQG)XUDQV

Complex, 75 PCDD congeners, 135PCDF congeners,

Very low <few µg kg-1 Very persistentHalf life several years

None Root retentionFoliar absorptionMinimal root

Possible into milk/tissues

�3&''�)V� Low water solubility, highlylipophilic and semi-volatile

Strongly adsorbed by soil O.M. Uptake and translocation Via soil ingestionLong half-life

Organochlorines pesticides Varied, lipophilic to hydrophilic,some volatile

<Few mg kg-1 Slow> 1 yearLoss by volatilisation

None Root retentionTranslocation not importantFoliar absorption

Via soil ingestion persistent intissues

Monocyclic aromatics Water soluble and volatile <1-10 mg kg-1 Rapid Moderate Limited due to low persistenceRapidly metabolised

Rapidly metabolised

Chlorobenzenes Water soluble/volatile to lipophilic <0.1-50 mg kg-1 Lower mol wt types lost byvolatilisationHigher mol wt types persistent

High to low Possible via roots and foliageMaybe metabolised

Important for persistentcompounds

Short-chained halogenatedaliphatics

Water soluble and volatile 0-5 mg kg-1 Lower mol wt types lost byvolatilisationHigher mol wt types persistent

Moderate Foliar absorptionPossible translocation

Low

Aromatic and alkyl amines Water soluble and low volatility 0-1 mg kg-1 Slow High Possible LowPhenol Varied, lipophilic high water

solubility and volatile0-5 mg kg-1 Rapid Moderate to

lowPossible via roots and foliage None

O.M., organic matter; mol wt: molecular weight

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3$+V��3RO\F\FOLF�DURPDWLF�K\GURFDUERQV�

3URSHUWLHV�DQG�PDLQ�FKDUDFWHULVWLFV

PAHs are composed of 2 to 7 aromatic rings associated in a compact way. They are mostly foundunder a liquid form. PAHs are numerous. Among others, the following compounds may bementioned: naphtalene, polyphenyls acenaphtene, phenanthrene, fluorene, fluoranthene, pyrene,benzo(a)pyrene. An example of a PAH chemical structure (fluorene) is presented below.

Naphtalene is used in the colouring industry, as a component in wood treatment products and inmothballs. The polyphenyls are used as refrigerating fluid or as fungicide in the paper industry.PAHs are also generated as by products of incomplete combustion in certain industries in whichcarbon and hydrogen are pyrolysed: iron and steel industry, rubber industry etc. They are producedunder mixed form, and their relative proportion in the mixture could enable to trace their origin.

1DSKWDOHQH is the most soluble compound in water, the most volatile and the most biodegradableof the PAH compounds. Other PAH compounds however are LQVROXEOH� LQ� ZDWHU�� OLWWOHELRGHJUDGDEOH�DQG�KDYH�D�KLJK�DIILQLW\ for sludge’s organic matter. Their characteristics of littlebiodegradable and lipophilic compounds increase with molecular weight.

2UJDQLF�FRPSRXQGV�FRQVWDQWV 3$+V

3Z From 0,00027 to 32

.RZ From 107 to 1010

+F From 4,9 10-4 to 5,3 10-8

+DOI�OLIH 1 week to 10 years

3$+V�7R[LFLW\

PAHs are no polar, lipid soluble compounds that may be absorbed via the skin, lungs or digestivetract. Once absorbed, these compounds are distributed to all tissues, but become particularlyconcentrated in those organs with a KLJK�OLSLG�FRQWHQW.

PAHs can be acutely toxic, but JHQHUDOO\� DW� YHU\� KLJK� GRVHV, making acute systemic toxicityobservable in some animal tests, but not likely to occur in humans, except in industrial context.

1DSKWDOHQH� LV� QRW� KLJKO\� WR[LF. On the contrary, EL�� DQG� SRO\SKHQ\OV� KDYH� DQ� DFWLRQ� RQ� WKHQHUYRXV�V\VWHP� as they are lipophilic. They also have an impact RQ�WKH�OLYHU. Some of them havebeen classified as SRVVLEOH� FDUFLQRJHQLF, like Benzo-a-pyrene which is assumed to be the mosttoxic of the PAHs. Some others PAH have a carcinogenic effect after chemical activation throughenzymes in the body.

2ULJLQ�LQ�VOXGJH

There are three sources of PAH in sludge:- PAHs are contained in exhaust gas and in the runoff of raining water on roads,

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- PAHs are generated in the fumes of industrial thermal units and may reach the soil throughraining water,

- PAHs are also found in industrial effluents.

PAHs can concentrate strongly in sludge and are little degraded by biological processes of watertreatments.

According to data available in the literature and provided in appendix 2, sludge can containbetween 0.018 and 10 mg/kg DM of PAHs in EU Member States.

%HKDYLRXU�LQ�VRLO

Most PAHs are YHU\� SHUVLVWHQW� LQ� VRLOV. Their half-life can reach until 10 years. They also areslowly biodegraded. PAHs are relatively insoluble in water and are therefore absorbed to theparticulate phase, especially the organic matter. Loss from soil may be due to photodegradation, orvolatilisation (mainly for 2 and 3 ringed PAHs).

7UDQVIHU�WR�ZDWHU

PAHs compounds have VWURQJ�ELQGLQJ�SURSHUWLHV especially on soil organic matter and relativelypoor water solubility. In this connection, the ULVN� RI� OHDFKLQJ of these substances to the groundwater is considered to be UHODWLYHO\�VPDOO.

8SWDNH�E\�SODQWV

Uptake of PAHs, under field conditions is fairly well documented. Four main routes for uptakehave been identified, namely the uptake from the soil solution by the roots, the adsorption to theroots, the foliar uptake from volatilised PAHs from the soil surface, and the foliar uptake fromatmospheric deposition. The last route has been identified as the main one, even in areas wheresludge has been applied [DEPA 1995]. The high rate of absorption by the soil reduces thebioavailability of the compound and therefore its possible transfer to the roots.

*HQHUDOO\�3$+�XSWDNH�E\�FURSV�LV�ORZ and does not represent a risk for the human food chaineven when sludge is applied to lipid rich root crops (especially carrots), a worst case condition ofPAH exposure.

PAH absorption is virtually nil for ray grass and soya but does occur in carrots and radishes(particularly in the epidermis of the roots in both cases) and in potatoes (in the tubercles).

The concentration factors7 are between 0.006 and 0.024 for all the PAHs in carrot roots, 0.01 to0.02 for benzo(a)pyrene in radish roots and 0.02 to 0.05 for benzo(a)pyrene in spinach leaves.

PAHs exhibit higher levels of transfer to plants than PCBs.

8SWDNH�E\�OLYHVWRFN

No uptake by livestock of PAHs was observed from experiments according to the literatureexamined.

7 Defined as the ratio between the level observed in the plant and the level observed in the soil [in terms of

dry material]

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Only a few studies are available which deal with the effects of PAHs on terrestrial micro-organisms, plants and soil living fauna. The Danish EPA [1997] summarised data concerning theEffect and No-Effect concentrations of PAHs on terrestrial organisms and plants. The results arepresented below. It must be stressed that the results refer to studies performed under differentconditions and protocols: various different soil types, organisms and duration are taken intoaccount, the effects studied (mineralisation, nitrification, growth, mortality etc.) are different andthe impact level on the population may vary according to the experiment. It is thereforerecommended to refer to the publication of the Danish EPA.

Moreover, this review refers mainly to short-term studies, as little information is availableconcerning the long-term effects of PAHs.

2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

Microorganisms 25-1000 100-2000

Plants 8.3-2000 25-4000

Invertebrates 57-2000 10-4500

+XPDQ�H[SRVXUH�OHYHO

,Q�DFFRUGDQFH�ZLWK�WKH�DIRUHPHQWLRQHG��LW�PD\�EH�DVVXPHG�WKDW�WKHUH�DUH�YHU\�IHZ�WUDQVIHUVRI�3$+V�WR�WKH�HQYLURQPHQW�PHGLD�DQG�WKH�IRRG�FKDLQ��7KHUHIRUH��KXPDQ�H[SRVXUH�OHYHO� WRVOXGJH�ERUQH�3$+V�LV�OLNHO\�WR�EH�ORZ�

The consumption of barbecued meat and smoked fish represents a much more massive route foringesting PAHs.

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3URSHUWLHV�DQG�PDLQ�FKDUDFWHULVWLFV�RI�3&%

PCB is a group of substances obtained by chlorination of biphenyls. There are about 200 differentkinds of PCB, so-called congeners, differentiated by their level of chlorination. The chemicalstructure is shown in the figure below.

PCBs are not naturally present in the environment and used to be incorporated in inks or asdielectric or heat-exchange fluid, and may have a lot of other industrial uses: lubrication, woodprotection, paints… They are however ubiquitous in the environment, but their production has beenstopped in the 70’s, and their level in the environment has gradually fallen in the last years[Sweetman and Jones 2000]. PCB’s primary transport route is atmospheric transport.

2UJDQLF�FRPSRXQGV�FRQVWDQWV 3&%

3Z variable

.RZ From 2,4 104 to 1,3 106

+F From 3,2 10-4 to 3,8 10-3

+DOI�OLIH Several years

The following table summarises some half-life values that have been observed for some congenersin the soil upper layers.

&RQJHQHU +DOI�OLIH�YDOXH�LQ�GD\V��\HDU�

PCB 28 490 (1,3)

PCB 52 3500 (9,6)

PCB 101 to 180 14 000 (38)

7R[LFLW\

Higher chlorinated PCB mixtures have been shown to be FDUFLQRJHQLF� LQ� ODERUDWRU\� DQLPDOH[SHULPHQWV.

Recent research also indicates that exposure to PCBs may cause UHSURGXFWLYH� DQGQHXURGHYHORSPHQWDO� FKDQJHV in exposed laboratory animals and in some people withenvironmental exposure to PCBs. They also may have a teratogenic action, as well as impacts onthe liver and thyroid.

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Some researches have addressed the question to know if those effects are due to the PCBs or toimpurities in the commercial preparations such as pentachlorodibenzofurans. It has to be noted thatPCBs generate PCDD/F in some conditions, when burnt for instance.

They also have the propensity to DFFXPXODWH�LQ�WKH�HQYLURQPHQW�DQG�LQ�DGLSRVH�WLVVXHV�

2ULJLQ�LQ�VOXGJH

PCBs come from the industry and from oils. They also come from everyday products such as paperand alimentation.

PCB content in sludge varies between 0 and 250 mg/kg DM in Member States.

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PCBs, especially highly chlorinated ones, are reputed to remain in the soil for long periods, sinceWKHLU�ELR�GHJUDGDWLRQ�DQG�PRELOLW\�OHYHOV�DSSHDU�WR�EH�ORZ. Their degradation pathways in soilwere not found.

PCBs possess a low vapour pressure but, nevertheless, their poor water solubility makesvolatilisation a significant loss mechanism for these compounds. Volatilisation of PCBs decreaseswith the increasing chlorination of the compound.

These compounds are VWDEOH� SK\VLFDOO\�� FKHPLFDOO\� DQG� ELRORJLFDOO\. They are OLSRSKLOLF andhave a tendency to concentrate in sludge and therefore in the organic material in the soil. They willbe therefore slower degraded in soil rich in organic matter. Despite the biodegradation that can beobserved in the soil and the partial volatilisation, these compounds are among the environmentallypersistent compounds found nowadays forming a diffuse background in the environment.

In Sweden, the observed level in soil of seven individual congeners were below the limit ofdetection except in one case 3 µg/kg DM and the sum of all PCBs was 25 µg/kg DM [Swedishenvironmental protection agency, 1996].

In the North of Germany (NRW, 1991), average level in agricultural area was 2,2 µg/kg DM in the0-10 cm layer for 6 of the most toxic compounds, 14 µg/kg DM for all of them.

In United Kingdom, observed levels from 7 to 10 µg/kg DM have been reported (Wilson HW�DO.,1997).

7UDQVIHU�WR�ZDWHU

PCBs can be found in surface water. PCBs transferred by runoff are bound to the solid phase of thesoil (rather than the liquid phase) and the concentration exported is directly linked to theconcentration in soil.

Considering the physical-chemical properties of PCBs, those compounds are QRW�DVVXPHG�WR�OHDFKWR�WKH�JURXQGZDWHU��The�Danish EPA [1997] reported very low levels of leaching documented inseveral studies. Tucker HW�DO� [1975]8 found less than 0.05% of the applied PCBs in the leachate.Moza HW�DO� [1976]9 established that only 0.2 % of the applied dichlorobiphenyl had reached a depthof 40 cm. two years after application to loamy sand.

8 Tucker HW� DO.; Migration of polychlorinated biphenyls in soil induced by percolating water; Bulletin of

Environmental Contamination and Toxicology 13, 86-93; 19759 Moza HW�DO.; Fate of 2,2’-dichlorobiphenyl-14C in carrots, sugar, and soil under outdoor conditions; Journal

of agricultural food chemistry, 24, 881-884; 1976

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8SWDNH�E\�SODQWV

Uptake of PCB by plants under field conditions is fairly well documented DQG�DSSHDUV�WR�EH�YHU\OLPLWHG��However, some publications reported that some compounds may be taken up by plants,those observations concerning mainly low chlorinated compounds. It was indeed observed that thetransfer factor decreases with increasing degree of chlorination [Offenbacher, 1992]. As fordioxins, it is possible that VRPH�FURSV�WDNH�XS�3&%�IURP�VRLO. Cortical layer of carrots for instanceconcentrates those compounds, as they are relatively fatty tissues.

$EVRUSWLRQ of PCBs is virtually nil for maize (in any part of the plant), lettuce, spinach, haricotbeans, sugar beet, grains of wheat or barley and fescue. It is very low in wheat straw and rape. It ismore significant in potatoes (in the skin of the tubercles but not the flesh) and carrots.

PCBs exhibit ORZHU�OHYHOV�RI�WUDQVIHU�WR�SODQWV�WKDQ�3$+V.

The known concentration factors for PCBs in maize and beet are 0.001 and 0.041 respectively.

8SWDNH�E\�OLYHVWRFN

Experiments in this area are quite rare. They essentially deal with the effects of PCBs on cattle anddemonstrate:

- An increase in the concentration of PCBs in the milk from cows fed on forage grown on landwhere residual sludge has been spread.

- An accumulation of PCBs in the fat, and particularly in the milk, but not in the muscles.

Cows grazing on sludge-amended soil seem to consume 0.22 µg of sludge-borne PCB per day dueto direct ingestion of soil. This can result in an increase in PCB concentrations in tissue fat andmilk fat by 0.00009 µg/g fat [Nilsson 1996]. The amount of PCB the animals might ingest due toconsumption of plants that have taken up or adsorbed PCB vaporised from the soil cannot becalculated, as the data are insufficient.

The level of contamination of PCB in animal tissues increases with the level of chlorination of thePCBs. The maximal concentration of PCBs in milk fat was four to five times larger than the dietarycontent.

The contribution from sludge to meat and dairy products seems to be below 1 % of the total PCBcontent in these foodstuffs [Nilsson 1996].

(FRWR[LFRORJ\

Only a few studies are available dealing with the effects of PCBs on terrestrial micro-organisms,plants and soil living fauna. The Danish EPA [1997] summarised data concerning the Effect andNo-Effect concentrations of PCBs on terrestrial organisms and plants. The results are presentedbelow. It must be stressed that the results refer to studies performed under different conditions andprotocols: various different soil types, organisms and duration are taken into account, the effectsstudied (mineralisation, nitrification, growth, mortality etc.) are different and the impact level onthe population may vary according to the experiment. It is therefore recommended to refer to thepublication of the Danish EPA.

Moreover, this review refers mainly to short-term studies, as little information is availableconcerning the long-term effects of PCBs.

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2UJDQLVP 12(&PJ�NJ��

(&PJ�NJ��

Microorganisms* 1 - > 100 1 - 50

Plants 2 - 100 100 - 1000

Invertebrates 500 - 2000 115 - 1000

* Only one study

+XPDQ�H[SRVXUH

PCBs are highly soluble in lipids and, because of slow metabolism and excretion rates,bioconcentration and biomagnification in the top predators in the food-chain may occur.

According to a Swedish study [Nilsson 1996], distribution of sewage sludge for soil improvementmay increase the PCB concentrations in meat and dairy products, but is unlikely to affectsconcentrations in fish and drinking water. Distribution of sludge would lead to an increase by about0,1 percent in milk products and by about 0,5 percent in meat products. Therefore, VOXGJH�ERUQH3&%�VHHPV�WR�FRQWULEXWH�YHU\�OLWWOH�WR�WKH�WRWDO�KXPDQ�H[SRVXUH�WR�3&%.

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3&''V���3&')V�SRO\FKORULQDWHG�GLEHQ]RGLR[LQV���GLEHQ]RIXUDQV�

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Dioxins and furans are not very different in their structure. They are constituted of two chlorinatedBenzene rings linked by a dioxin (two oxygens) or furan (one oxygen) cycle. As for PCBs, thereare different levels of chlorination. Therefore, about 200 congeners exist. An example of thechemical structure of a furan congener is shown below.

PCDD/Fs are ubiquitous in the environment at extremely low levels. In the industry, PCDD/Fs arenot used as such, but are by-products of combustion reaction. They appear for instance during themanufacture of insecticides, herbicides, antiseptics, disinfectants and wood preservatives. They arenaturally produced in very small amounts following forest fires for instance.

PCDD/Fs are usually generated during combustion of products containing organic matter andchlorine. Therefore one significant potential source of dioxins and furans is the incineration ofwaste. They are destroyed at high temperature, but they may reform during the cooling phase atabout 400 – 500 °C.

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Among those compounds, 17 are considered as toxic, and the most important ones are 2, 3, 7, 8TCDD. All the toxic congeners do have at least 4 chlorine atoms at the following positions: 2, 3, 7,8.

It is considered that GLR[LQV�DQG� IXUDQV�KDYH� WKH� VDPH� WR[LFLW\. The lethal dose of the 2,3,7,8TCDD is about a few µg/kg by certain species. There is considerable debate to know if a thresholdfor effects on human health exists.

The position of the WHO is that the Tolerable Daily Intake is 10 pg per kg body weight per day.Even as trace, it generates chloracne and impacts the skin pigmentation. It has also impacts onliver, is FDUFLQRJHQLF and WHUDWRJHQLF. The half-life of the dioxins and furans in the human body isabout 6 years and they are lipophilic. They are therefore FXPXODWLYH.

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Toxicities of the different congeners are different, and they have been affected by a coefficient inreference to the 2,3,7,8 TCDD. Coefficients vary between 0,001 and 0,5. (See table below). Thecomposition of a given mixture of PCDD/Fs compounds enables to identify and trace its possibleorigin.

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1. Tetrachlorodibenzodioxin 2,3,7,8 TCDD 1

2. Pentachlorodibenzodioxin 1,2,3,7,8 PeCDD 0,5

3. Hexachlorodibenzodioxin 1,2,3,4,7,8 HxCDD 0,1

4. Hexachlorodibenzodioxin 1,2,3,7,8,9 HxCDD 0,1

5. Hexachlorodibenzodioxin 1,2,3,6,7,8 HxCDD 0,1

6. Heptachlorodibenzodioxin 1,2,3,4,6,7,8 HpCDD 0,01

7. Octachlorodibenzodioxin OCDD 0,001

8. Tetrachlorodibenzofuran 2,3,7,8 TCDF 0,1

9. Pentachlorodibenzofuran 2,3,4,7,8 PeCDF 0,5

10. Pentachlorodibenzofuran 1,2,3,7,8 PeCDF 0,005

11. Hexachlorodibenzofuran 1,2,3,4,7,8 HxCDF 0,1

12. Hexachlorodibenzofuran 1,2,3,7,8,9 HxCDF 0,1

13. Hexachlorodibenzofuran 1,2,3,6,7,8 HxCDF 0,1

14. Hexachlorodibenzofuran 2,3,4,6,7,8 HxCDF 0,1

15. Heptachlorodibenzofuran 1,2,3,4,6,7,8 HpCDF 0,01

16. Heptachlorodibenzofuran 1,2,3,4,7,8,9 HpCDF 0,01

17. Octachlorodibenzofuran OCDF 0,001

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Three origins have been identified:- As by-products of the industry, they can appear in industrial effluents,- They are present in the environment under a diffuse form for instance after deposition on soil

and plants. They can enter the sewage system after running off from street and roofs,- PCDD/Fs are present in the commercial preparations of insecticide products.

PCDD/Fs can concentrate in sludge. Jones [1997] indicated that sludge loss may happen throughbiological degradation or volatilisation, but that dioxins could also be generated during thewastewater treatment process because of biological activity.

As given in appendix 2, PCDD/Fs levels in European sludge ranges from below 0.01 to around 200ng/kg DM.

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These compounds are SK\VLFDOO\��FKHPLFDOO\��ELRORJLFDOO\�stable and are OLSRSKLOLF. They tend toconcentrate in sludge and subsequently in the organic material of the soil, and a very strongadsorption by soil is to be expected. In general, dioxins and furans will be found in the topsoil, andpenetration to the deeper soil layers will only be possible under exceptional conditions (high water

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flow, preferential flow channel) [Danish EPA 1997]. They constitute a diffuse background ofpollution in the environment.

The observed levels of PCDD/Fs have been reported to be between 1 and 1,6 ng TEQ/kg DM inSweden. It may be calculated that if 1 ton DM/ha/year with a TEQ content of 37,7 ng/kg DM,would be applied, it would take 30 to 50 years to double the TEQ content in soil if breakdown ofdioxins and furans was assumed to occur [Swedish environmental protection agency, 1996].

In a British study [Jones 1997], the median total PCDD/Fs concentration in 65 rural soils was 335ng/kg, and reached 1440 ng/kg in 19 urban soils. This would indicate that levels to be observed arehigher in urban areas.

Their fate in soil is not well known. Volatilisation is a potentially important loss mechanism forPCDD/Fs in soil. Photolysis could also happen, but there is no consensus on this phenomenon.Lastly, biodegradation was observed in laboratory conditions, but it is assumed that it would bemuch slower in field conditions, especially for high-chlorinated species. Hydrolysis and oxidationare also thought to be insignificant in soils. Lastly, the formation of irreversibly bound, non-extractable residues in soil could be of importance, but has not been enough documented yet [Jones1997].

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As mentioned above, dioxins and furans are highly lipophilic and are thus QRW�H[SHFWHG�WR�OHDFKIURP�VRLO�LQWR�ZDWHU�UHVHUYRLUV��RU�RQO\�FRQFHUQ�YHU\�OLWWOH�DPRXQWV�RI�WKH�FRPSRXQGV�DSSOLHG[Department of the environment and UK water industry research, 1995]. This has been supportedby field observation [Jones 1997], but leaching was observed in some particular cases, in thepresence of surfactants for instance.

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The dioxins and furans found in upper parts of the plant seem to come from the air. It is explainedby atmospheric deposition to foliage and adsorption of contaminants from the gaseous phase whichare derived principally from other sources [Witte, 1989]. Reischl HW�DO� [1989] and Sacchi HW� DO�[1986] showed that YRODWLOLVDWLRQ�DQG�DEVRUSWLRQ�E\� WKH�XSSHU�SDUWV�RI� WKH�SODQWV�ZDV�PRUHLPSRUWDQW� WKDQ� URRW� XSWDNH� SURFHVVHV in shoot tissue contamination with PCDD/Fs.Volatilisation of dioxins depend from its level of chlorination. Uptake into potatoes and carrotskins has been demonstrated. Jones [1997] concluded that WKH�LQIOXHQFH�RI�VOXGJH�DPHQGPHQW�RQWKH� 3&''�)� FRQFHQWUDWLRQ� LQ� DERYHJURXQG� SODQW� WLVVXHV� FDQ� EH� LJQRUHG� LQ� WKH� SDWKZD\DQDO\VLV�RI�KXPDQ�H[SRVXUH�

Prinz HW�DO� concluded that the root uptake could be a significant contamination route. Howeverother observation reported that peel represents an effective barrier to contamination for root cropplants. It is also assumed that the lipophilic character of those compound induces a tight binding tosoil particles, reducing their transfer to the roots. Uptake by roots presents a BCF of 0.05.

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Distribution of sludge is expected to increase animal’s exposure to PCDD/Fs via soil ingestion.

The PCDD/Fs pass into the blood via the gastrointestinal system at varying absorption ratesaccording to the congener involved. When the compounds are poorly chlorinated, the absorptionrate is higher. Those compounds are not metabolised, and are stored in the adipose tissues or maybe eliminated into the milk.

Drinking water and inhalation have been shown to be negligible intake sources [Jones 1997].

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Only a few studies are available dealing with the effects of PCDD/Fs on terrestrial micro-organisms, plants and soil living fauna. The Danish EPA [1997] summarised data concerning theEffect and No-Effect concentrations of PCBs on terrestrial organisms and plants. The results arepresented below. It must be stressed that the results refer to studies performed under differentconditions and protocols: various different soil types, organisms and duration are taken intoaccount, the effects studied (mineralisation, nitrification, growth, mortality etc.) are different andthe impact level on the population may vary according to the experiment. It is thereforerecommended to refer to the publication of the Danish EPA.

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Microorganisms 0.05 – 2.4 0.5*

Plants 10* N/A

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* Only one study

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The exposure routes to dioxins are numerous. It can be inhaled from air, but can also be ingestedafter deposition of dioxins and furans and their concentration in plant or animals’ fat and milk. As alipophilic compound, another exposure route concerning babies of relevance is the intake of breastmilk. Use of sewage sludge as a fertiliser might contribute in increased TEQ concentrations in meatand dairy products, whereas the concentrations in fish and drinking water are probably not affectedby sewage sludge. The exposure to sewage sludge will therefore depend from the diet.

The total contribution of sludge borne PCDD/Fs seems to be small. However, due to theirphysicochemical properties, dioxins are also persistent in the human body and concentrate alongthe food chain. Therefore even low exposure levels are of importance.

Wild HW�DO. [1994], performed an assessment of human exposure to sludge-borne PCDD/Fs. One ofthe main conclusions was that application of sludge to crops will not significantly influence humanexposure to PCDD/Fs due to the inefficiency of transfers from soil to plant tissues. In contrast,transfers of dioxins and furans from sludge-amended pasture to livestock via ingestion of soil andsludge adhering to vegetal are critical with regard to human exposure, and these transfer processesare the principal pathways influencing the human diet.

A quantitative assessment was also made, assuming that the human diet is composed of productsgrown or reared exclusively on soil amended with sludge at a rate of application of 10 t DM/ha. Itwas assessed that background exposure to 2,3,7,8-substituted PCDD/Fs was 0.2027 ng I-TEQ.day-1

and it appeared that the human exposure to PCDD/Fs increased by between 15-400 % according tothe congener compared to background exposure. However, the hypotheses were highly unrealistic.On the contrary, when considering that only 1 to 3 % of the diet originates from sludge-amendedsoil (i.e. the percentage of UK agricultural land currently amended with sludge), the increase in theexposure to PCDD/Fs was below 0.1 % compared to the background exposure. Therefore, sub-surface injection of sludge rather than surface spraying would clearly reduce the potential ofPCDD/Fs to enter the human food chain.

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A draft Commission regulation proposes to set maximum levels for some heavy metals in foodstuffas described in the following table10. It must be stressed that those limit values have been set basedupon what is achievable using good working practice. The Scientific Committee for Food howeverrecommended that those values should be as low as reasonably achievable.

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1. Fat of Cow’s milk (liquid, as consumed) 3

2. Fat of poultry meat 3

3. Fat of beef meat 5

4. Fat of pork meat 2

5. Egg fat 5

6. Fish (whole product) 3

10 Draft Commission regulation setting maximum levels for certain contaminants in foodstuff amending

commission regulation EC n° 194/97 of 31 January 1997. ENTR/5799/99 – rev 1 - EN

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DEHP belongs to the esters of phtalates, which are all esters of the phtalic acid. It accounts for overhalf of the total use of phtalates and is also the most well studied of these compounds.

DEHP may be used as a plasticiser, with application in the construction and packaging industries(for instance in the production of PVC), as well as in the production of components of medicaldevices.

The detection of DEHP may be disturbed when using plastic chemical devices, as they can befound in such products.

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This organic compound is little persistent and lipophilic.

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Studies have shown WHVWLFXODU�DWURSK\ and QHRSODVWLF�HIIHFWV RQ�WKH�OLYHU�LQ�UDWV�DQG�PLFH. Theycan also LQGXFH�D�WHUDWRJHQLF�HIIHFW, even if they do not have a teratogenic effect themselves.

Actually, only few studies are available for toxicity on humans. They concluded to the need toreduce the exposure arising from the use of plastic devices.

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DEHP-like compounds originate from effluents of the plastic industry and from compounds inplastic matter, which can be transferred in the wastewater.

DEHP and phtalates content in sludge is between 20 and 660 mg/kg DM in EU countries.

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DEHP has a low water solubility and a high octanol-water partition coefficient. Therefore itsabsorption in soil is high. Under aerobic conditions, micro-organisms degrade DEHP relativelyeasily, explaining the relatively low soil concentration reported in the relevant literature [DanishEPA 1997].

DEHP seems to accumulate in soil after sludge distribution, but only when very large amounts ofsludge are applied. At normal doses, DFFXPXODWLRQ�GRHV�QRW�RFFXU because of the very short half-

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life of the compound under aerobic conditions. Under anaerobic conditions, DEHP is very slowlyor not at all degraded.

Like in the preceding cases, degradation pathway of those compounds in soil was not found in theliterature. It cannot be excluded that certain partially broken down metabolites might have the sameeffects as DEHP.

The observed levels of DEHP in soil are below the detection limit in Sweden (< 1 mg/kg DM)[Swedish environmental protection agency, 1996].

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Increased concentrations of DEHP in ground water were observed after distribution of 100 times ofthe normal amount of sludge. This does however not reflect normal practices. No data was foundconcerning the leaching of DEHP to groundwater after fertilisation with normal amounts of sludge.It must be reminded that DEHP is rather fast degraded in soil and are lipophilic, permitting toassume that only little leaching occur.

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Uptake of DEHP by plants is not very well documented

Considering the available data, uptake of DEHP by plants DSSHDUV�WR�EH�ORZ, because of its rapidbiodegradation in soil. Despite treatment with very large amounts of sludge (100 200 tonsDM/ha/year), the amount of DEHP in the crops (rye, fodder rape seed and English rye-grass) wasbelow the detection limit (<1 mg DEHP/kg DM). The Danish EPA [1997] reported thataccumulation of airborne phtalates in plant cuticles may be of importance, whereas the root uptakefrom soil is negligible. It must be borne in mind that DEHP is lipophilic and therefore stronglybinds to the soil organic fraction.

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The DEHP seems to be ingested primarily with concentrated feed rather than with grass and hay orwith soil. Because DEHP is contained in the concentrated food, animal held indoors also ingest thesubstance.

Exposure to Phtalates can also occur via the drinking water.

Further studies are also required in order to calculate the BCF between fodder and tissue or milkfat.

DEHP does not seem to accumulate in animal tissues.

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Phtalates are considered as moderately to highly toxic in relation to aquatic organisms. Despite thelack of data, the Danish EPA [1997] assumed this could be the same for terrestrial organisms, asthe main exposure route to DEHP is the water phase. Several phtalates are also suspected ofendocrine disruption.

Despite the few available studies, the Danish EPA [1997] summarised data concerning the Effectand No-Effect concentrations of phtalates on terrestrial organisms and plants. The results arepresented below. It must be stressed that the results refer to studies performed under different

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conditions and protocols: various different soil types, organisms and duration are taken intoaccount, the effects studied (mineralisation, nitrification, growth, mortality etc.) are different andthe impact level on the population may vary according to the experiment. It is thereforerecommended to refer to the publication of the Danish EPA.

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It is assumed that the main exposure route for terrestrial organisms to DEHP is the water phase. Anefficient metabolism and excretion of phtalates is observed in many higher organisms e.g. fish,earthworms and man. Therefore a biomagnification of DHP in the higher trophic levels of theterrestrial ecosystem is not likely [Danish EPA].

It is difficult to assess how much of the human total exposure to DEHP and phtalates is due tosludge spreading on arable lands and subsequent contamination of food-stuffs and drinking water.

%DVHG�RQ�WKH�YHU\�OLPLWHG�GDWD, it would seem that uptake into plants is small, and that DEHP isnot accumulated in animal tissues. If this is the case, distribution of sludge ought to contribute verylittle to DEHP human exposure (even though it cannot be set in relation to the total exposure inEurope, which is not clearly known).

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NPE are surface-active agents used in detergents and washing powders.

Nonylphenol is formed in wastewater treatment plants when incoming nonylphenolethoxylates areconverted during digestion of the sludge.

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Actually available data is insufficient, but WHQVLRDFWLYHV�DUH�QRW�KLJKO\� WR[LF�DV� VXFK. However,their PHWDEROLWHV after degradation are often more toxic and harder to degrade. There is actually alack in knowledge about toxicological effects and definition of these metabolites.

Several studies show that NP and other alkylphenols have HVWURJHQLF�HIIHFWV�ERWK�LQ�YLWUR�DQG�LQYLYR. It is likely that the observed effects occur due to binding to estrogens receptors. Thissubstance has estrogens perturbing effects in rats at low doses. A US study concluded that1RQ\OSKHQRO� LV� D�PDOH� DQG� IHPDOH� UHSURGXFWLYH� WR[LFDQW at concentrations 650 ppm. NP canchange sex of a few fishes if they are exposed to high levels. NPE may also be metabolised to NP.

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The main origin of those compounds in sludge is the daily and industrial use of detergents. Theirmetabolites can appear in the sludge during its biological evolution. They concentrate in sludge butundergo rapid biodegradation under aerobic conditions.

A survey conducted among all of Sweden’s wastewater treatment plants showed median values forNP of 45, 35 and 32 mg/kg DM [Nilsson 1996].

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Most studies indicate a short half-life for NP in soil, suggesting a reduced risk of accumulation.The Danish EPA [1997] mentions that in laboratory studies and some field studies, it has beenfound that all, or a large fraction of the NPs applied through sludge application disappear from soilwithin 50-100 days. These studies also reported that such an important degradation only takes placeunder aerobic conditions and if microbial activity is not inhibited. Studies also observed thatmicrobial metabolism would be the main route for degradation of nonylphenols in soil [DanishEPA 1997].

NP addition to soil did not affect the nitrification process. It can be therefore assumed that it did notaffect the bacterial activity of the soil. The ministry of environment of Denmark [1998] reportedhowever a slow biodegradation.

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The surfactant property of such compounds can increase the solubility of other organic micro-pollutants and thus their bioavailability for living organisms in the soil and leaching propensity.

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A field study conducted in Malmö in 1994 examined the effects of large amounts of sludge (100times the recommended amounts; NP content 50-280 mg/kg DM) incorporated into arable soil. TheNP levels in groundwater remained undetectable (<2 µg/L) [Nilsson 1996].

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NP/NPE uptake by plants is not extensively documented in the literature.

$FFRUGLQJ� WR� 1LOVVRQ� >����@�� 13� GRHV� QRW� VHHP� WR� EH� WDNHQ� XS� E\� SODQWV�� 6HYHUDO� VWXGLHVFRQFOXGHG�WKDW�LQWHUQDO�FRQFHQWUDWLRQV�LQ�VSULQJ�EDUOH\�JUDLQV�ZHUH�LQGHSHQGHQW�RI�ZKHWKHURU� QRW� WKH� VRLO� ZDV� FRQWDPLQDWHG� ZLWK� 13� >'DQLVK� (3$@�� RU� WKDW� QR� LQFUHDVH� LQ� WKH� 13FRQWHQW� RI� JUDLQV�ZDV� REVHUYHG� IROORZLQJ� VOXGJH� DSSOLFDWLRQ� >����@�� +RZHYHU�� QRW� HQRXJKGDWD� LV�DYDLODEOH. Uptake of NP by plants could occur because of the tensidic properties of thecompound. It was also mentioned that one metabolite of NP and NPE degradation could have agreater water solubility, and thus could more easily migrate to plants, or be leached. Moreinformation would be needed concerning the degradation of those compounds.

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Little information has been published concerning NP/NPE uptake by livestock. The amount of NPoriginating from sewage sludge and other sources and consumed with fodder by meat and dairystock seems very small. The main source of NP/NPE for livestock seems to be drinking water,which most likely is not polluted with NP/NPE originating from sludge. Judging from the fewavailable data, NP does not accumulate in animal tissue, and is eliminated rapidly.

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The Danish EPA [1997] summarised data concerning the Effect and No-Effect concentrations ofnonylphenol on terrestrial organisms and plants. The results are presented below. It must bestressed that the results refer to studies performed under different conditions and protocols: variousdifferent soil types, organisms and duration are taken into account, the effects studied(mineralisation, nitrification, growth, mortality etc.) are different and the impact level on thepopulation may vary according to the experiment. It is therefore recommended to refer to thepublication of the Danish EPA.

Publications concerning Nonylphenol mainly refer to short-term experiments. Possible long-termeffects are not covered in the literature.

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Concerning NP/NPE, it seems that the main exposure route is the consumption of drinking water,which is likely not affected by the agricultural use of sewage sludge. Assuming a dailyconsumption of 2 litres per person, humans are exposed to 0,58 µg of nonylphenol and 5,8 µg ofnonylphenolethoxylates. In some food, nonylphenol content was found to be below the detectionlimit. However total exposure to NP/NPE is not known.

Keeping in mind that nonylphenol is rapidly degraded in soil, and that uptake by plants is assumedto be low, the contribution of the agricultural use of sewage sludge may be considered as very low.

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LAS and NPE are surface-active agents used in detergents and washing powders.

LAS is easily degraded under aerobic conditions. Annual worldwide consumption of LAS isapproximately 2.106 tons and EU consumption is assumed to be about 300 000 tons.

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Actually available data is insufficient, but WHQVLRDFWLYHV�DUH�QRW�KLJKO\� WR[LF�DV� VXFK. However,their PHWDEROLWHV after degradation are often more toxic and harder to degrade. There is currently alack of knowledge concerning the toxicological effects and definition of these metabolites.

LAS can cause allergies and have effects on VNLQ� SLJPHQWDWLRQ. Some metabolites such asaliphatic amines can have HIIHFWV�RQ�WKH�OLYHU��NLGQH\V�DQG�KHDUW��EXW�DUH�QRW�FDUFLQRJHQLF.

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The main origin of these compounds in sludge is the daily and industrial use of detergents. Theirmetabolites can appear in the sludge during its biological evolution. They concentrate in sludge butundergo rapid biodegradation under aerobic conditions.

Due to these chemical properties, LAS levels are much higher in anaerobic digested sludge than inaerobic digested sludge. LAS sludge concentration is therefore between 10 and 19,000 mg/kg DM,as summarised by Jensen [1999] (see following table).

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Denmark 19 Various 11 – 16 100

Germany 8 Anaerobic digested 1 600 – 11 800

Germany 10 Aerobic 182 – 432

Italy 1 Anaerobic digested 11 500 – 14 000

Spain 3 Anaerobic digested 12 100 – 17 800

Spain 2 Non-treated 400 - 700

Switzerland 10 Anaerobic digested 2 900 – 11 900

UK 5 Anaerobic digested 9 300 – 18 800

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Sludge-bound LAS are UDSLGO\�DQG�FRPSOHWHO\�ELRGHJUDGHG in DHURELF soil, and a half-life valueranging from 7 to 26 days has been assessed. In anaeobic conditions, LAS degradation is howeverslower. DEPA [1995] reports that surfactants may be affected by different chemical and physicalprocesses such as photolysis, hydrolysis, ionisation, oxidation/reduction, ligand exchange, sorptionand biodegradation, of which sorption and biodegradation are of practical significance.

LAS adsorbs quite strongly to solids, or will be degraded rapidly under aerobic soil conditions.Thus LAS are not expected to accumulate to toxic levels in soil when sludge with a typical LAScontent (e.g. below 6,000 mg/kg DM) is applied using the normal amounts of landspreading. It hasbeen reported that branched anionic surfactants are more slowly degraded than straight chainedsurfactants. Degradation of LAS is influenced by temperature, water content, availability ofoxygen, the amount of LAS supplied as well as the position of the benzene ring. Several studieswere carried out, documenting the level of LAS found in soil after sludge application. Results varywidely, from 0 to 45 µg/g.

The surfactant property of such compounds can increase the solubility of other organic micro-pollutants and thus their bioavailability for living organisms in the soil and leaching propensity.

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No data was found for LAS leaching to groundwater.

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Log Kow is given as 3.7 for LAS, and the substance may therefore be expected to be taken up andtransported in plants. An experiment by Sweetman HW�DO (1994) on potential accumulation of LASin potatoes, cabbage, leeks and carrots showed however, that the concentration of LAS in planttissues was below the analytical limits of detection.

Two laboratory studies were found documenting the effect of sludge-borne LAS on crops[Unilever 1987 and Thomas HW�DO� 1988 in Mieure 1990]. The results of the first study are shown inthe table below:

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6XQIORZHU 1 to 1000 91

0XQJ�EHDQ 1 ; 10 ; 100 84

1000 75

6RUJKXP 1 ; 10 ; 100 78

1000 69

In the second study, sludge borne LAS application generally resulted in promotion (up to 55%)rather than retardation of plant growth.

Mieure [1990] also performed a literature survey concerning the effects of the LAS on some cropsfollowing irrigation. The results are summarised in the table below.

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Pea Growth inhibition at 50 mg/L Lichtenstein HW�DO� (1967)

Paddy rice Production inhibition at 50 mg/L Taniyama HW�DO� (1978)

Potted rice Yellowing of leaf blade at 50 mg/L Taniyama HW�DO� (1978)

Rice seedlings 5 mg/L promoted growth ;40 mg/L Inhibited growth

Wakiuchi HW�DO� (1988)

Barley, Beans,Tomato

Non effect at 40 mg/LGrowth enhancement at 25 and 40 mg/L

Lopez-Zavala HW�DO�(1975)

Barley, Radish,Pea, Tomato,Lettuce

No effect at 100 mg/Lretarded growth at 1000 mg/L

Gilbert HW�DO� (1988)

Radish Critical concentration : 10 mg/L Takita (1982)

Cucumber Growth retardation at 100 mg/Lno effect at 10 mg/L

Gilbert HW�DO� (1988)

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Data is lacking concerning LAS transfer to livestock.

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The Danish EPA [1997] summarised data concerning the Effect and No-effect concentrations ofLAS on terrestrial organisms and plants. The results are presented below. It must be stressed thatthe results refer to studies performed under different conditions and protocols: various different soiltypes, organisms and duration are taken into account, the effects studied (mineralisation,nitrification, growth, mortality etc.) are different and the impact level on the population may varyaccording to the experiment. It is therefore recommended to refer to the publication of the DanishEPA.

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2UJDQLVPV12(&mg.kg-1

(&mg.kg-1

Microorganisms 33-59 56-135

Plants 16-1000 90-1000

Invertebrates 235-613 500-1333

Mieure [1990] reported that the toxicity to aquatic organisms has been quantified, and thatacceptable margins of safety exist between effect levels and the very low levels of LAS found insurface waters. Earthworms did not appear to be affected by high level of LAS application to soil.

The main effects of surfactants in general are the disruption of biomembranes and the denaturationof proteins. Toxic action of surfactants seems to be due to reactions at the cell surface, consisting ofdepolarisation of the cell membrane by the adsorption of surfactants, resulting in a decreasedabsorption of nutrients and oxygen consumption, as well as in a decreased release of toxicmetabolic products.

The specific toxicity of LAS depends on the position of the benzene ring. Terminal ring positionresults in higher toxicity compared to a central placement of the ring. Toxicity also increases withchain length as long as the surfactant remains soluble.

Branched anionic surfactants show less aquatic toxicity than straight-chained anionic surfactants. Inthe same time branched anionic surfactants are more slowly degraded than straight-chainedsurfactants. DEPA [1995] observed that very little information was available concerning theterrestrial toxicity of LAS.

It appeared from the review of the experiments that the effects of surfactants have been ofstimulating as well as of inhibiting character. A stimulation of micro-organisms has often beencorrelated to the ability of using the surfactant as a carbon source [DEPA 1995].

+XPDQ�H[SRVXUH

Very little data is available about LAS transfer ability. LAS are not persistent in soil and arequickly degraded. Plant uptake is assumed to be low.

Mieure [1990] concluded that the safety margins appeared to be more than adequate to protectterrestrial plants and animals from harm by using LAS during irrigation with secondary sewagesludge elements or upon soil fertilisation with sewage sludge.

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%DFWHULDBacteria are primitive cells without nucleus or developed cytoplasmic organelles. They present agreat variety, and more than 250 types and many thousands of species have been listed. Some ofthem may grow in very adverse conditions.

%DFWHULD�IRXQG�LQ�VOXGJH

Bacteria found in sludge are numerous and include 6DOPRQHOOD� VSS���(��FROL� �LQ�SDUWLFXODU�(�FROL2������and�/HSWRVSLUD�VSS�for instance��A detailed summary is given by WRc [2001] and is givenin the main part of this report.

6DOPRQHOOD is the most important one because of the risk on grazing animals [WHO, 1981].6DOPRQHOOD VSS. is naturally present in the environment.

(VFKHULFKLD�FROL is naturally present in human and animals digestive tract. About 140 serologicalgroups have been listed, of which only a few are pathogenic (for instance (��FROL O157) when theirproportion increases. They are useful indicators of faecal pollution of water. Observed levels of (�FROL in the environment are important.

/HSWRVSLUD in sludge is more likely to occur as a result of post-treatment contamination from theurine of infected rodents rather than from sewage itself.

6KLJHOOD� VSS�� 3VHXGRPRQDV�� <HUVLQLD�� &ORVWULGLXP�� /LVWHULD�� 0\FREDFWHULXP�� 6WUHSWRFRFFXV and&DPSK\OREDFWHU may also be found.

Bacteria levels in organic waste are presented in the table below [ADEME 1994].

1XPEHU�/LWUH /LTXLGPDQXUH

'DLU\VOXGJH

1R�GLVLQIHFWHGXUEDQ�VOXGJH

'LVLQIHFWHGXUEDQ�VOXGJH

$HURELF�EDFWHULD 3,5 106 6,2 106 7,3 107 3 103

6WDSK\ORFRFFXV 9 104 8 102 1 103 < 6

&ROLIRUPV 2 105 2,9 103 6,1 103 <6

6WUHSWRFRFFXV - 5,3 103 3,6 103 <6

6DOPRQHOOD + + + -

3URSHUWLHV

Bacteria are among the most sensitive pathogens to environmental conditions outside their host.Their number rapidly decreases when exposed to light, temperature decrease and desiccation.[Coker, 1983].

%HKDYLRXU�LQ�VRLO

Smith [1996] reported that 99% of VDOPRQHOOD and 99.9% of (VFKHULFKLD�FROL are retained withinthe first 3 cm of the soil.

Half-life of 6DOPRQHOOD varies according to the external conditions. When spread in summer, itshalf-life is between 424 to 820 days; when spread in winter, this reduces to 104 to 350 days[Strauch 1998]. Other sources mention that at typical levels of contamination in sludge, a 90 %reduction in Salmonella is observed within three weeks following sludge application [Pike anCarington, 1986, Sorber and Moore, 1987]. Turpin HW�DO� [1992] reported that sludge amended soil

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promoted antagonistic effects of soil micro-organisms increasing the rate of Salmonella die-off insoil.

3DWKRJHQV 6XUYLYDO�LQ�VRLO

Bacteria : salmonella, coliforms < 70 days (often < 20 d)

Source: WHO, 1989

%HKDYLRXU�RQ�SODQWV

Desiccation and sunlight cause a high mortality among bacterial pathogens adhering to the leavesof crop plants treated with sewage sludge (Coker, 1983).

3DWKRJHQV 6XUYLYDO�RQ�SODQWV

Bacteria : salmonella, coliforms < 100 days (often < 20 d)

Source: WHO 1989

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9LUXVHVViruses are not considered to be living organisms. They are made up of an inner core of nucleicacid and an outer protein coat. There are many types of viruses, differentiated by biochemicalcharacteristics such as the type of nucleic acid or protein coat. More than 120 different viruses maybe found in human faeces. All of them need living cells to reproduce themselves.

9LUXVHV�IRXQG�LQ�VOXGJH

Many types of viruses may be found in sludge such as� 3ROLRYLUXV�� (FKRYLUXV�� $GHQRYLUXV�5HRYLUXV��5RWDYLUXV��$VWURYLUXV��&DOFLYLUXV�and�3DUYRYLUXV. (QWHURYLUXVHV occur widely in sewagesludge. Hepatitis A virus may also be present [Bosch HW�DO�, 1986], which is a human specific virus.

There is no record of the human immunodeficiency virus (HIV) having been isolated from faeces,and epidemiological evidence shows that sewage and water have not been implicated in thetransmission of HIV [Pike, 1987]11.

9LUXV�VXUYLYDO�LQ�VRLO�DQG�SODQWV

Viral agents are retained by adsorption to soil particles. Adsorption level increases with increasingclay and organic matter content [Sorber and Moore, 1987]. Most viruses are retained in the top 2cm of soils, although a small proportion may penetrate more deeply.

Studies dealing with virus contaminated sludge exposed to natural rainfall showed limited or nomovement below depths of 0.5-1.25 m [Sorber and Moore, 1987].

Viruses are generally rapidly inactivated near soil surface. This may however depend ontemperature conditions.

Viruses are obligate intracellular parasites and do not replicate outside of the appropriate host.Consequently, their number eventually decreases in the soil environment, irrespective ofconditions, because they are not adapted to survive outside of the host animal for long periods.Their survival has been assessed to 3 months.

Viruses may be eliminated from vegetation within 24 days [Larkin HW�DO�, 1976].

3DWKRJHQV 6XUYLYDO�LQ�VRLO 6XUYLYDO�RQ�SODQWV

HQWHURYLUXVHV < 100 days (often < 20 d) < 60 days (often < 15 d)

Source: WHO, 1989

11 Although prions are not viruses, it should be noted here that there is no evidence suggesting that a BSE

(Bovine Spongiform Encephalopathy) transmission factor would be present in sludge.

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3DUDVLWHVA parasite is an organised living body, which needs a host to grow or reproduce himself during oneor many steps of his life cycle. Different types of parasites exist, such as helminths, mushrooms orprotozoa. Some of them may develop a cyst or egg stage, in order to resist to environmental stress.

Helminths are worms and include Cestodes, Trematodes or Nematodes. Protozoa are unicellularorganisms, most of them living in aqueous environment.

3DUDVLWHV�IRXQG�LQ�VOXGJH

Different types of parasitic worms and protozoa may be found in sludge. Among Helminths,$VFDULV and WDHQLD may be cited, as well as (QWDPRHED or *LDUGLD as Protozoa.

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Sorber and Moore [1987] considered that mechanical straining was the most important factorgoverning parasite transport through soil. The transport of protozoa and helminths in soils appearsto be more limited than for bacteria or viruses. Indeed, available literature suggests that the ova ofparasites and the cysts of protozoa are retained at the point of sludge introduction.

Kowal [1983] documented that survival times for protozoa in soil were typically about two days,possibly extending to a maximum period of ten days.

However parasites’ eggs or cysts are incontestably the longest survivors in soil – one to two yearsin certain favourable circumstances. On average, loss of viability, and therefore of infectiousness,occurs within a few weeks.

3DWKRJHQV 6XUYLYDO�LQ�VRLO

+HOPLQWKV: $VFDULV��7DHQLD�VDJLQDWD Several months

3URWR]RD: (QWDPRHED�KLVWRO\WLFD < 20 days (often < 10 d)

Source: WHO, 1989

%HKDYLRXU�RQ�SODQWV

Immature $VFDULV ova do not survive on vegetation more than 35 days [Rudolphs HW� DO�, 1951],although mature or hatching ova, which occur frequently in sludge, are more able to survive toadverse conditions [Engelbrecht, 1978].

Taenia ova are susceptible to desiccation, and viability of both 7DHQLD and $VFDULV is reducedthrough fungal attack and degeneration [Silverman, 1955; Jones HW�DO�, 1979].

Protozoan cysts are sensitive to desiccation and only survive a few days on vegetation under dryingconditions [Coker, 1983 ; Sorber and Moore, 1987].

3DWKRJHQV 6XUYLYDO�RQ�SODQWV

+HOPLQWKV: $VFDULV��7DHQLD�VDJLQDWD < 60 days (often < 30 d)

3URWR]RD: (QWDPRHED�KLVWRO\WLFD < 10 days (often < 2 d)

Source: WHO, 1989

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$SSHQGL[���7\SLFDO�FRPSRVLWLRQ�RI�DQLPDO�PDQXUHDQG�VOXUU\

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FDWWOH�PDQXUH FDWWOH�VOXUU\ SLJ�PDQXUH SLJ�VOXUU\ SRXOWU\�PDQXUH

'U\�VROLGV���� 20 - 50 1 - 18 25 1 - 18 30 - 60

�$JULFXOWXUDO�YDOXH��NJ�W�����IUHVK�ZHLJKW�

2UJDQLF�PDWWHU 130 - 150 10 - 107 160 34 - 70

1�7RWDO 4 - 9 2 - 18 5 - 7 2 - 16 14 - 29

1�1+� 1.5 – 3.1 0.6 – 2.2 0.7 – 2.5 2.1 – 3.6 5.3 – 6.1

3�2� 1 - 8 1 - 12 1 – 7.6 1 - 12 12.4 - 25

.�2 2.5 - 12 2 - 15 4 – 4.1 2 - 9 8.4 - 21

&D2 1.8 – 4.2 0.3 – 4.5 6 1.4 – 6.7 14.5 – 40.5

0J2 0.5 – 1.5 0.3 – 1.5 2.5 0.5 – 1.8 1.2 – 4.2

1D�2 1.3 0.8 0.8 – 0.9 9.2

�2OLJR�HOHPHQWV��PJ�NJ�'6�

,URQ��)H 4000 1500

0DQJDQHVH��0Q 400 600

&REDOW��&R 0.7 1.9 0.5

�+HDY\�PHWDOV��PJ�NJ�'6�

&DGPLXP���&G 0.1 – 0.4 0.2 – 0.6 0.7 0.2 – 0.5 0.38 – 0.8

&KURPLXP��&U 0.4 – 2.6 2.6 - 15 1.9 2.4 – 1.8 4.1 - 24

&RSSHU���&X 15 - 75 31 - 70 346 180 - 574 59 - 100

0HUFXU\���+J 0.17 0.05

1LFNHO���1L 1 - 14 3.3 - 14 5 3.2 - 17 4.9 - 17

/HDG���3E 1.4 – 4.3 4.3 – 5.8 2.8 <1 - 12 2.2 - 4

=LQF���=Q 63 - 175 132 - 750 387 403 - 919 403 - 556

6HOHQLXP���6H 0.2 0.6 0.6

Source : WRc 2001, Survey of wastes spread on land, Draft final report.

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0 50 100 150 200 250 300 350 400 450 500

1XPEHU�RI�\HDUV

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Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

86 limit value in soil

soil accumulation

soil accumulation and plant uptake

soil accumulation, plant uptake and runoff

,PSDFW�RI�VOXGJH�TXDOLW\�DQG�TXDQWLW\

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0 50 100 150 200 250 300 350 400 450 500

1XPEHU�RI�\HDUV

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Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

86 limit value in soil

1 ton /ha/year

3 tons/ha/year

2 tons/ha/year

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0 50 100 150 200 250 300 350 400 450 500

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Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

86 limit value in soil

0,3 ppm in soil

1 ppm in soil

0,1 ppm in soil

,QIOXHQFH�RI�VOXGJH�TXDOLW\�DQG�FOD\�FRQWHQW�RI�VRLO

0

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0 50 100 150 200 250 300 350 400 450 500

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Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

30 % clay in soil

50 % clay in soil

10 % clay in soil86 limit value in soil (10 % clay)

86 limit value in soil (30 % clay)

86 limit value in soil (50 % clay)

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0

2

4

6

8

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0 50 100 150 200 250 300 350 400 450 500

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0HWDO�OHYHO�LQ�VRLO��NJ�KD�\HDU�

Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

86 limit value in soil

1750 kg/ha

7000 kg/ha

3500 kg/ha

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Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

86 limit value in soil

90 % humidity in plant

50 % humidity in plant

15 % humidity in plant

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0

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0 50 100 150 200 250 300 350 400 450 500

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Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

86 limit value in soil

0,1 transfer factor

0,3 transfer factor

0,5 transfer factor

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Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

15 cm repartition depth

35 cm repartition depth

25 cm repartition depth

86 limit value in soil (35 cm)

86 limit value in soil (25 cm)

86 limit value in soil (15 cm)

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0

2

4

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0 50 100 150 200 250 300 350 400 450 500

1XPEHU�RI�\HDUV

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Metal level in sludge of the 86

directive

3,8 mg/kg DM

0,4 mg/kg DM

Metal level in soil

Limit value : 3 ppm in soil

Limit value : 2 ppm in soil

Limit value : 1 ppm in soil