Annex II: Nanomaterials in the Danish Environment

Transcription

1 Annex II: Nanomaterials in the Danish Environment Modelling exposure of the Danish environment to selected nanomaterials Annex II f environmental project No. 1639, 2015

2 Title: Auths: Annex II: Environmental Exposure to Nanomaterials in Denmark. Fadri Gottschalk 2 Bernd Nowack 2 Carsten Lassen 1 Jesper Kjølholt 1 Frans Christensen 1 1 COWI A/S 2 Swiss Nano Modelling Constium (SNMC) Published by: The Danish Environmental Protection Agency Strandgade Copenhagen K Denmark Year: 2015 Disclaimer: When the occasion arises, the Danish Environmental Protection Agency will publish repts and papers concerning research and development projects within the environmental sect, financed by study grants provided by the Danish Environmental Protection Agency. It should be noted that such publications do not necessarily reflect the position opinion of the Danish Environmental Protection Agency. However, publication does indicate that, in the opinion of the Danish Environmental Protection Agency, the content represents an imptant contribution to the debate surrounding Danish environmental policy. Sources must be acknowledged.

3 Contents 1. Introduction System geometry Total engineered nanomaterial mass transfer and fate system f Denmark Subsystem waste incineration plant Exposure concentrations in and natural Introduction Photostable and other nano titanium dioxide (TiO2) Photocatalytic titanium dioxide (TiO2) Zinc oxide (ZnO) Silver (AgNP) Carbon nanotubes (CNT) Nano-copper carbonate (CuCO3) Nano-CeO Quantum dots Carbon black... 59

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5 1. Introduction This Annex II shows the model architecture (Chapter 2) and provides all the modelled results (Chapter 3) that belong to the main rept. However, this Annex II limits itself by presenting results and does not give any text-based guide f the reader f interpreting evaluating the content. F that kind of infmation the reader may consult the cresponding main rept (Rept 2) and its first annex (Annex I). The latter contains an overview on the model parameters used. In the main rept the used methodology and the modelled results were presented and discussed. The system geometry is shown in Chapter 1. This geometry reflects the target system "Denmark" containing the most relevant and environmental : sewage treatment plants (STP) and waste incineration plants (WIP), of material landfill and recycling processes, as well as water, sediments, air and soil environments. An insight is given also into the architecture of the subsystem "waste incineration plants". The environmental exposure concentrations (predicted environmental concentrations (PEC) are presented f Denmark by assuming the studied engineered nanomaterial homogeneously distributed in the different listed above. The following engineered nanomaterials have been investigated: - Silver (Ag) - Titanium Dioxide (TiO2) (rutile and anatase) - Zinc Oxide (ZnO) - Carbon Nanotubes (CNTs) - Copper carbonate (CUCO3) - Zero Valent Iron (ZVI) 1 - Cerium Oxide (CeO2) - Carbon Black (CB) - Quantum Dots (QDs) Each specific section f each nanomaterial contains six Tables with modelled PEC-values f and natural : Table 1 (of each nanomaterial specific section) provides the results of sewage treatment effluents, waste mas incinerated, bottom ash of waste mas incinerated and fly ash of waste mass incinerated. Table 2 gives the results f the terrestrial environment (agricultural soils, natural soils, urban soils and sewage treatment sludge treated soils) while tables 3 and 4 show all the PECs f the aquatic covering fresh water and their sediments as well as the cresponding marine (and air). Tables 5 and 6 fecast nanomaterial PECs in fresh and marine sediments as well as in the different soil types f the time period until 2014 and F this nanomaterial all the results that mostly focus on local scenarios are shown in the main rept (Rept 2).

6 2. System geometry The system geometry is shown in the figures 1 and 2. Such geometry reflects the target system Denmark. 2.1 Total engineered nanomaterial mass transfer and fate system f Denmark FIGURE 1. SYSTEM GEOMETRY WITH BOXES AND ENGINEERED NANOMATERIAL (ENM) FLOWS, DEPOSITION AREAS (LOWER LEFT HAND CORNER), TRANSFORMATION MASS (LOWER RIGHT HAND CORNER) AND FLOW RATES (VALUES IN THE MIDDLE OF THE BOXES AND SUB-BOXES). THE SUBSYSTEM WASTE INCINERATION PLANT (WIP) IS SHOWN IN DETAIL IN THE NEXT FIGURE (FIGURE 2). VALUES FOR ALL THESE 109 PARAMETERS FOR THE COMPUTER BASED STOCHASTIC SIMULATIONS ARE GIVEN IN ANNEX I OF THE MAIN REPORT.

7 2.2 Subsystem waste incineration plant FIGURE 2. SYSTEM GEOMETRY FOR WASTE INCINERATION PLANTS (WIP) WITH BOXES AND ENGINEERED NANOMATERIAL (ENM) FLOWS IN T/A, DEPOSITION AREAS (LOWER LEFT HAND CORNER), TRANSFORMATION MASS (LOWER RIGHT HAND CORNER) AND FLOW RATES (VALUES IN THE MIDDLE). EXEMPLARY VALUES FOR ALL THESE WIP PARAMETERS DERIVED FROM THE COMPUTER BASED STOCHASTIC SIMULATIONS ARE GIVEN FOR NANO-ZNO IN FIGURE 3.

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9 3. Exposure concentrations in and natural 3.1 Introduction The Tables 1-53 summarize the predicted concentrations f a selection of engineered nanomaterials in: a) Residues of the main (sewage treatment sludge, waste mass, bottom ash and fly ash of waste incineration); b) The main natural environments surface waters (fresh water, sea water, sewage treatment effluents), air, different soil types (agricultural, natural, urban and sludge treated soils) and sediments (fresh water and sea water sediments). F soil and sediment results the concentration increase is presented given a conservative scenario of no engineered nanomaterial transfmation/degradation in such. The sludge treated soil concentrations purely reflect the STP sludge contribution on such soil exposure. In der to assess the total exposure in such fertilized areas one can add the generic agricultural soil PECs to the ones of the pure sludge based contribution. F these soil and sediment we also predict concentrations after an engineered nanomaterial (ENM) deposition in soils beginning in 2000 and ending in the beginning of the year 2014 and Zero use and release and of such ENM were considered f the time befe the year Since then a linear increase of ENM deposition on soils was computed by scaling the deposition calculated in this wk f the year We indicated in those tables the 2.5, 50 (median) and 97.5 % quantiles as well as modal values (the most frequent Monte Carlo computer simulation output). F photostable and other nano-tio2 the results (probability density functions) on the load into different natural and is shown (Figure 3) as an exemplary case. F nano-zno the results (median values) on the mass transfer (Figure 4) in waste incineration plants are shown as well as an exemplary case.

10 Density Density Density Density Density 3.2 Photostable and other nano titanium dioxide (TiO 2) Freshwater Seawater t/a Freshwater sediments Seawater sediments t/a Soils Sludge treadet soils t/a Landfills Recycling plants Sewage treatment plant Waste incineration plant t/a t/a FIGURE 3. PROBABILITY (DENSITY) DISTRIBUTIONS OF THE ANNUAL LOAD T/A OF PHOTOSTABLE AND OTHER NANO-TIO2 INTO THE DIFFERENT NATURAL AND TECHNICAL COMPARTMENTS. TABLES 1-6.

11 PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR PHOTOSTABLE AND OTHER NANO-TiO2 DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge mg/kg Waste mass incinerated mg/kg Bottom ash of waste incineration mg/kg Fly ash of waste incineration mg/kg

12 TABLE 2 Agricultural soils µg/kg Natural soils µg/kg Urban soils µg/kg Sludge treated soils µg/kg

13 TABLE 3. Surface water (fresh water) µg/l Sea water 4.04E E-04 µg/l 3.95E Sewage treatment effluent µg/l Sediments (fresh water) accumul µg/kg

14 TABLE 4. Sediments (sea water) µg/kg Air 1.3E E-04 µg/m3 1.4E E-04

15 TABLE 5. green curves results f 2014 red curves results f 2020 Agricultural soils µg/kg Natural soils µg/kg Urban soils µg/kg Sludge treated soils µg/kg

16 TABLE 6. green curves results f 2014 red curves results f 2020 Sediments (sea water) µg/kg Sediments (fresh water) µg/kg

17 3.3 Photocatalytic titanium dioxide (TiO2) TABLES PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR PHOTOCATALYTIC NANO-TiO2 DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge mg/kg Waste mass incinerated mg/kg Bottom ash of waste incineration mg/kg Fly ash of waste incineration mg/kg

18 TABLE 8. Agricultural soils µg/kg Natural soils µg/kg Urban soils µg/kg Sludge treated soils µg/kg

19 TABLE 9. Surface water (fresh water) 4.7E E-04 µg/l Sea water 3.6E E-05 µg/l 3.2E E-05 Sewage treatment effluent µg/l Sediments (fresh water) µg/kg

20 TABLE 10. Sediments (sea water) µg/kg Air 7.7E E-04 µg/m

21 TABLE 11. green curves results f 2014 red curves results f 2020 Agricultural soils µg/kg Natural soils µg/kg Urban soils µg/kg Sludge treated soils µg/kg

22 TABLE 12. green curves results f 2014 red curves results f 2020 Sediments (sea water) µg/kg Sediments (fresh water) µg/kg

23 3.4 Zinc oxide (ZnO) FIGURE 4. SYSTEM GEOMETRY OF THE WASTE INCINERATION PLANT (WIP) WITH STUDIED COMPARTMENTS AND ENGINEERED NANOMATERIAL (ZnO) FLOWS IN T/A, ACCUMULATION OR TRANSFORMATION MASS (POSITIVE OR NEGATIVE MASS VALUES IN THE BOXES) SHOWN AS ROUNDED MEDIANS. SUCH ROUNDED IN THIS CASE MEDIAN VALUES (EXTRACTED FROM ALL THE MONTE CARLO SIMULATIONS) REPRESENT HIGH PROBABILITY RESULTS AT ALL DIFFERENT STAGES OF THE WIP WITHOUT PRECISELY ILLUSTRATING IN THE FIGURE MASS-BALANCE FROM A WHOLE PERSPECTIVE.

24 TABLES PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR NANO-ZnO DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge Almost no nano-zno is remaining in nanofm in this compartment. mg/kg Waste mass incinerated mg/kg Bottom ash of waste incineration mg/kg Fly ash of waste incineration mg/kg

25 TABLE 14. Agricultural soils µg/kg Natural soils µg/kg Urban soils µg/kg Sludge treated soils See please comments f STP sludge. µg/kg

26 TABLE 15. Surface water (fresh water) 8.6E E-04 µg/l 2.7E E-02 Sea water 5.6E E-05 µg/l 5.8E E-04 Sewage treatment effluent 0 Almost no nano-zno is ending up in µg/l nanofm in this compartment. Sediments (fresh water) µg/kg

27 TABLE 16. Sediments (sea water) µg/kg Air 5.20E E-05 µg/m3 6.39E E-04

28 TABLE 17. green curves results f 2014 red curves results f 2020 Agricultural soils µg/kg Natural soils µg/kg Urban soils µg/kg Sludge treated soils See please comments f STP sludge. µg/kg

29 TABLE 18. green curves results f 2014 red curves results f 2020 Sediments (sea water) µg/kg Sediments (fresh water) µg/kg

30 3.5 Silver (AgNP) TABLES PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR NANO-Ag DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge * µg/kg Waste mass incinerated µg/kg Bottom ash of waste incineration µg/kg Fly ash of waste incineration µg/kg *inconclusive, bipolar ( pluripolar) insignifact difference to median

31 TABLE 20. Agricultural soils ng/kg Natural soils ng/kg Urban soils ng/kg Sludge treated soils * ng/kg *inconclusive, bipolar ( pluripolar) insignifact difference to median

32 TABLE 21. Surface water (fresh water) 0 * ng/l Sea water 0 2.5E-04 ng/l 2.8E Sewage treatment effluent ng/l Sediments (fresh water) 0 * µg/kg *inconclusive, bipolar ( pluripolar) insignifact difference to median

33 TABLE 22. Sediments (sea water) µg/kg Air ng/m

34 TABLE 23. green curves results f 2014 red curves results f 2020 Agricultural soils ng/kg Natural soils ng/kg Urban soils ng/kg Sludge treated soils ng/kg

35 TABLE 24. green curves results f 2014 red curves results f 2020 Sediments (sea water) µg/kg Sediments (fresh water) 0 0 * * µg/kg *inconclusive, bipolar ( pluripolar) insignifact difference to median

36 3.6 Carbon nanotubes (CNT) TABLES PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR CNT DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge µg/kg Waste mass incinerated µg/kg Bottom ash of waste incineration µg/kg Fly ash of waste incineration µg/kg

37 TABLE 26. Agricultural soils ng/kg Natural soils ng/kg Urban soils ng/kg Sludge treated soils ng/kg

38 TABLE 27. Surface water (fresh water) 1.8E ng/l Sea water 2.2E E-05 ng/l 7.0E E-04 Sewage treatment effluent ng/l Sediments (fresh water) µg/kg

39 TABLE 28. Sediments (sea water) µg/kg Air ng/m

40 TABLE 29. green curves results f 2014 red curves results f 2020 Agricultural soils ng/kg Natural soils ng/kg Urban soils ng/kg Sludge treated soils ng/kg

41 TABLE 30. green curves results f 2014 red curves results f 2020 Sediments (sea water) µg/kg Sediments (fresh water) µg/kg

42 3.7 Nano-copper carbonate (CuCO3) TABLES PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR NANO-COPPER CARBONATE DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge mg/kg Waste mass incinerated mg/kg Bottom ash of waste incineration mg/kg Fly ash of waste incineration mg/kg TABLE 32.

43 Agricultural soils µg/kg Natural soils µg/kg Urban soils µg/kg Sludge treated soils µg/kg

44 TABLE 33. Min (2.5% Surface water (fresh water) 1.2E-04 * µg/l 2.4E E-03 Sea water 2.0E E-05 µg/l 3.9E E-05 Sewage treatment effluent µg/l Sediments (fresh water) * µg/kg *inconclusive, bipolar ( pluripolar) insignifact difference to median

45 TABLE 34. Sediments (sea water) µg/kg Air 4.60E E-05 µg/m3 2.05E E-05

46 TABLE 35. green curves results f 2014 red curves results f 2020 Agricultural soils µg/kg Natural soils µg/kg Urban soils µg/kg Sludge treated soils µg/kg

47 TABLE 36. green curves results f 2014 red curves results f 2020 Sediments (sea water) µg/kg Sediments (fresh water) * * µg/kg *inconclusive, bipolar ( pluripolar) insignifact difference to median

48 3.8 Nano-CeO 2 TABLES PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR NANO-CEO2 DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge µg/kg Waste mass incinerated µg/kg Bottom ash of waste incineration µg/kg Fly ash of waste incineration µg/kg TABLE 38.

49 Agricultural soils ng/kg Natural soils ng/kg Urban soils ng/kg Sludge treated soils ng/kg

50 TABLE 39. Surface water (fresh water) ng/l Sea water 3.15E E-04 ng/l 5.04E Sewage treatment effluent ng/l Sediments (fresh water) µg/kg

51 TABLE 40. Sediments (sea water) µg/kg Air ng/m

52 TABLE 41. green curves results f 2014 red curves results f 2020 Agricultural soils ng/kg Natural soils ng/kg Urban soils ng/kg Sludge treated soils ng/kg

53 TABLE 42. green curves results f 2014 red curves results f 2020 Sediments (sea water) µg/kg Sediments (fresh water) µg/kg

54 3.9 Quantum dots TABLES PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR QUANTUM DOTS (QD) DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge 3.58E µg/kg Waste mass incinerated µg/kg Bottom ash of waste incineration µg/kg Fly ash of waste incineration µg/kg

55 TABLE 44. Sewage treatment effluent ng/l Sludge treated soils pg/kg

56 TABLE 45. Sediments (sea water) 4.71E E-08 µg/kg 9.74E E-07 Sediments (fresh water) 2.54E E-07 µg/kg 1.32E E-05

57 TABLE 46. green curves results f 2014 red curves results f 2020 Sludge treated soils 6.7E E E E-04 ng/kg

58 TABLE 47. green curves results f 2014 red curves results f 2020 Sediments (sea water) µg/kg Sediments (fresh water) µg/kg

59 3.10 Carbon black TABLES PREDICTED ENVIRONMENTAL CONCENTRATIONS (PEC) IN THE FORM OF PROBABILITY (DENSITY) DISTRIBUTIONS FOR CARBON BLACK (CB) DERIVED FROM COMPUTER BASED STOCHASTIC SIMULATIONS ON NANOMATERIAL RELEASE TO AND SCENARIOS FOR FATE/RESIDENCE TIME IN TECHNICAL AND NATURAL COMPARTMENTS. Sewage treatment sludge mg/kg Waste mass incinerated mg/kg Bottom ash of waste incineration mg/kg Fly ash of waste incineration mg/kg

60 TABLE 49. Agricultural soils mg/kg Natural soils mg/kg Urban soils mg/kg Sludge treated soils mg/kg

61 TABLE 50. Surface water (fresh water) µg/l Sea water µg/l Sewage treatment effluent µg/l Sediments (fresh water) * mg/kg *inconclusive, bipolar ( pluripolar) insignifact difference to median

62 TABLE 51. Sediments (sea water) mg/kg Air µg/m

63 TABLE 52. green curves results f 2014 red curves results f 2020 Agricultural soils mg/kg Natural soils mg/kg Urban soils mg/kg Sludge treated soils mg/kg

64 TABLE 53. green curves results f 2014 red curves results f 2020 Sediments (sea water) mg/kg Sediments (fresh water) * * mg/kg *inconclusive, bipolar ( pluripolar) insignifact difference to median

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66 Nanomaterials in the Danish environment The rept is Annex 2 to the rept ""Nanomaterials in the Danish environment. Modelling exposure of the Danish environment to selected nanomaterials". Strandgade 29 DK København K Tlf.: (+45) www. mst.dk