Electronic Supplementary Material

Title: Spatial and temporal trends of metals and arsenic in German freshwater compartments

Journal: Environmental Science and Pollution Research (ESPR)

Authors: Annette Fliedner*, Heinz Rüdel, Burkhard Knopf, Karlheinz Weinfurtner, Martin Paulus, Mathias Ricking, Jan Koschorreck

* Fraunhofer Institute for Molecular Biology and Applied Ecology (Fraunhofer IME), 57392 Schmallenberg, Germanyannette.fliedner@ime.fraunhofer.de

Table S1: Metals and arsenic in suspended particulate matter from the German ESB sampling sites, sampling period: 2005 – 2009 (exceptions: Danube: 2009; Saar: 2006-2009). Concentrations are given as µg/g dry weight. The highest mean value of every element is written in bold letters.

Water Sampling site

Value Arsenic Lead Cadmium Mercury Copper Nickel Zinc

Danube D1UIm

Range 6.96 25.38 0.54 148.7 36.68 26.52 171.0Median 6.96 25.38 0.54 148.7 36.68 26.52 171.0Mean n.d. n.d. n.d. n.d. n.d. n.d. n.d.SD n.d. n.d. n.d. n.d. n.d. n.d. n.d.

D2Kelheim

Range 9.01 23.37 0.34 222.0 41.20 28.13 180.3Median 9.01 23.37 0.34 222.0 41.20 28.13 180.3Mean n.d. n.d. n.d. n.d. n.d. n.d. n.d.SD n.d. n.d. n.d. n.d. n.d. n.d. n.d.

D3Jochenstein

Range 11.74 19.77 0.25 133.7 37.68 35.88 112.5Median 11.74 19.77 0.25 133.7 37.68 35.88 112.5Mean n.d. n.d. n.d. n.d. n.d. n.d. n.d.SD n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Elbe E1Prossen

Range 23.48- 38.58 68.05-113.3 1.66-3.06 790.0-1580 69.28-124.0 33.48-69.50 388.0-633.0Median 24.60 71.18 1.90 918.7 82.62 43.82 444.5Mean 27.38 81.05 2.06 1100 89.88 46.71 464.6SD 6.38 18.98 0.57 327.5 21.39 13.54 98.26

E2Zehren

Range 16.67-31.12 33.92-84.80 1.34-6.51 212.8-1039 29.22-87.32 15.65-59.50 229.5-773.8Median 25.15 56.53 3.36 649.7 67.82 35.52 588.5Mean 24.69 61.08 3.81 665.0 62.21 37.13 539.9SD 6.37 19.75 1.90 314.2 21.80 15.61 203.1

E3Barby

Range 14.82-27.95 93.50-122.5 3.12-4.90 1725-2850 80.50-101.3 33.78-45.88 725.5-1075Median 18.36 104.5 3.35 2065 86.67 36.32 867.0Mean 20.80 106.1 3.79 2099 87.90 38.24 863.1SD 5.48 12.38 0.82 455.6 8.02 4.93 135.2

E4Cumlosen

Range 20.30-24.68 49.87-71.85 2.38-8.63 1418-1925 62.12-81.05 19.62-32.92 441.8-640.2Median 20.72 62.23 3.62 1512 66.26 28.94 584.4Mean 22.09 62.15 4.39 1578 68.35 28.05 548.6SD 2.13 8.17 2.44 201.3 7.59 5.38 87.13

Table S1 (cont.): Metals and arsenic in suspended particulate matter from the German ESB sampling sites, sampling period: 2005 – 2009 (exceptions: Danube: 2009; Saar: 2006-2009). Concentrations are given as µg/g dry weight. The highest mean value of every element is written in bold letters.

Water Sampling site

Value Arsenic Lead Cadmium Mercury Copper Nickel Zinc

Elbe E5Blankenese

Range 17.65-20.15 39.82-52.60 0.24-5.49 785.2-996.5 40.92-49.80 22.13-27.33 244.3-341.5Median 19.45 44.00 1.47 929.0 42.00 23.35 290.3Mean 19.26 45.77 2.10 903.1 44.01 24.47 297.3SD 0.97 5.29 1.99 80.06 3.68 2.60 43.44

Mulde MUDessau

Range 91.48-111.5 125.8-150.5 9.13-12.33 956.0-1393 61.03-73.72 51.52-82.45 391.5-1043Median 106.3 137.0 10.21 1258 65.45 69.93 739.2Mean 101.9 138.5 10.61 1205 66.09 68.87 760.3SD 9.42 9.56 1.37 186.5 5.13 13.32 265.4

Saale SAWettin

Range 11.60-19.13 66.82-90.97 0.63-10.05 2078-4095 76.78-105.0 42.43-62.08 457.0-712.7Median 12.83 77.63 2.81 2342 86.03 53.88 555.3Mean 14.04 78.02 3.74 2674 89.58 53.13 563.1SD 3.02 8.67 3.65 812.0 11.21 7.18 106.9

Rhine R1Weil

Range 6.70-8.33 19.23-25.48 0.09-0.35 84.07-169.5 28.37-33.07 19.07-28.93 90.75-112.7Median 7.56 24.82 0.16 158.3 31.00 25.08 95.52Mean 7.45 23.37 0.19 135.7 30.81 24.31 98.87SD 0.61 2.59 0.10 39.49 2.24 3.95 8.41

R2Iffezheim

Range 8.07-9.66 24.13-29.03 0.23-0.45 212.7-275.5 40.10-45.37 24.17-34.00 120.3-133.8Median 9.15 28.53 0.29 243.8 42.53 33.30 129.5Mean 9.01 27.35 0.31 243.0 42.73 30.53 127.3SD 0.61 2.18 0.08 24.29 2.02 4.45 5.53

R3Koblenz

Range 7.80-9.63 22.10-29.72 0.19-0.48 199.8-258.3 30.87-38.83 19.52-28.92 117.2-153.0Median 7.99 24.80 0.25 210.7 35.13 22.55 139.0Mean 8.42 25.21 0.29 219.4 35.46 23.76 136.8SD 0.79 2.85 0.11 22.66 3.32 3.58 12.98

R4Bimmen

Range 11.70-12.45 47.05-57.33 0.67-1.70 353.5-552.0 46.47-59.10 26.98-37.15 281.0-588.5Median 11.97 51.12 0.85 391.5 52.95 35.33 284.8Mean 12.04 51.45 0.96 413.4 52.43 33.71 344.1SD 0.35 3.81 0.43 79.05 4.69 4.22 136.6

Table S1 (cont.): Metals and arsenic in suspended particulate matter from the German ESB sampling sites, sampling period: 2005 – 2009 (exceptions: Danube: 2009; Saar: 2006-2009). Concentrations are given as µg/g dry weight. The highest mean value of every element is written in bold letters.

Water Sampling site

Value Arsenic Lead Cadmium Mercury Copper Nickel Zinc

Saar S1Güdingen

Range 8.78-11.97 43.15-58.78 0.72-1.21 163.2-313.2 49.35-68.33 26.75-35.47 284.3-391.5Median 10.49 51.24 0.86 167.4 51.74 33.22 365.8Mean 10.43 51.10 0.91 202.8 55.29 32.16 351.9SD 1.34 6.41 0.21 73.62 8.80 4.09 47.22

S2Rehlingen

Range 13.58-17.47 54.27-69.22 0.89-1.79 228.3-278.8 69.98-89.38 38.25-47.32 390.2-636.5Median 14.28 66.54 1.10 253.5 70.66 43.77 529.9Mean 14.90 64.14 1.22 253.5 75.17 43.28 521.6SD 1.74 6.72 0.42 20.64 9.48 4.65 101.6

n.d. not determined

Table S2: Metals and arsenic in zebra mussels (Dreissena polymorpha) from the German ESB sampling sites. Concentrations are given as µg/g dry weight except for mercury (ng/g)

Water Sampling site and period

Value Arsenic Lead Cadmium Mercury Copper Nickel

µg/g dw µg/g dw µg/g dw ng/g dw µg/g dw µg/g dwLake Belau B

Lake Belau1997-2009

Range 6.20-7.81 0.10-0.53 0.18-0.56 32.57-76.50 8.59-21.90 6.32-18.97Median 6.66 0.20 0.28 43.02 11.78 11.00Mean 6.99 0.26 0.33 49.74 13.84 11.67SD 0.60 0.18 0.14 16.37 5.07 3.96

Danube D1UIm2003-2009

Range 2.56-3.62 0.45-0.86 0.61-0.88 37.72-60.68 12.67-18.93 7.36-17.70Median 2.90 0.80 0.72 53.78 17.04 14.05Mean 3.03 0.71 0.74 51.69 16.49 13.23SD 0.35 0.17 0.10 7.73 2.12 3.34

D2Kelheim2004-2009

Range 3.06-5.11 0.90-1.61 0.21-0.53 51.82-122.0 17.25-43.97 11.54-29.10Median 3.96 1.14 0.34 102.0 27.08 19.19Mean 3.99 1.18 0.36 92.36 28.44 19.42SD 0.67 0.28 0.12 30.51 9.93 6.14

D3Jochenstein2004-2009

Range 5.71-7.46 2.52-4.08 1.02-1.27 107.0-125.0 18.00-51.75 37.68-54.18Median 6.59 2.60 1.15 113.2 25.48 43.20Mean 6.63 2.92 1.15 114.6 29.34 45.64SD 0.66 0.66 0.11 7.86 12.96 7.67

Table S2 (cont): Metals and arsenic in zebra mussels (Dreissena polymorpha) from the German ESB sampling sites. Concentrations are given as µg/g dry weight except for mercury (ng/g)

Water Sampling site and period

Value Arsenicµg/g dw

Leadµg/g dw

Cadmiumµg/g dw

Mercuryng/g dw

Copperµg/g dw

Nickelµg/g dw

Elbe E1Prossen1999-2009

Range 4.40-7.66 2.37-4.98 0.44-1.18 80.23-216.2 13.47-20.28 18.73-28.82Median 6.17 3.40 0.61 120.7 16.60 22.60Mean 6.00 3.55 0.74 140.4 16.36 23.29SD 0.84 0.93 0.28 46.01 2.00 3.68

E2Zehren2000-2009

Range 2.79-5.87 2.02-13.98 0.52-6.40 150.7-271.7 11.80-24.75 5.44-22.45Median 4.59 4.43 0.87 215.8 19.30 12.48Mean 4.58 6.12 1.72 215.2 18.77 12.67SD 1.03 4.13 1.94 38.22 3.38 4.72

E3Barby1998-2009

Range 3.67-6.58 0.78-9.91 0.34-1.00 114.3-335.5 9.41-19.50 8.50-18.92Median 5.61 2.43 0.60 220.7 14.24 14.21Mean 5.57 2.93 0.56 204.0 14.25 14.50SD 0.90 2.40 0.19 70.33 2.49 3.10

E4Cumlosen1998-2009

Range 3.81-6.70 0.99-4.32 0.39-2.07 114.8-314.5 13.27-17.73 8.86-23.05Median 5.95 1.91 0.77 146.3 15.35 17.83Mean 5.56 2.12 0.93 164.1 15.41 17.10SD 1.00 0.94 0.48 59.28 1.38 4.61

E5Blankenese1995-2009

Range 7.04-12.78 2.25-5.26 0.92-2.36 163.6-328.6 19.08-33.07 14.90-42.57Median 9.42 3.79 1.13 244.0 27.20 25.86Mean 9.58 3.82 1.24 246.5 26.79 27.34SD 1.78 0.97 0.40 48.0 4.90 8.60

Table S2 (cont.): Metals and arsenic in zebra mussels (Dreissena polymorpha) from the German ESB sampling sites. Concentrations are given as µg/g dry weight except for mercury (ng/g)

Water Sampling site and period

Value Arsenicµg/g dw

Leadµg/g dw

Cadmiumµg/g dw

Mercuryng/g dw

Copperµg/g dw

Nickelµg/g dw

Rhine R1Weil1995-2009

Range 3.09-5.32 0.93-3.46 0.82-1.37 61.67-186.8 18.26-31.97 18.55-37.63Median 4.08 2.08 0.90 156.7 21.83 29.11Mean 4.13 2.12 0.98 140.5 24.11 28.17SD 0.82 1.08 0.20 47.32 5.67 6.58

R2Iffezheim1995-2009

Range 5.52-7.91 1.59-4.06 0.81-2.00 93.85-203.8 21.09-33.58 21.78-63.58Median 6.63 3.36 1.28 148.0 28.63 43.13Mean 6.67 3.00 1.34 148.1 27.98 42.90SD 0.98 1.27 0.57 46.51 5.46 22.10

R3Koblenz1995-2009

Range 3.73-6.13 1.77-6.36 0.66-2.12 54.82-155.8 18.87-42.30 10.02-37.51Median 4.70 3.19 1.00 88.37 27.35 20.66Mean 4.73 3.56 1.16 95.71 26.84 22.24SD 0.86 1.81 0.50 35.15 7.11 9.63

R4Bimmen1995-2009

Range 4.43-7.70 3.25-10.89 1.38-2.91 67.04-197.0 24.17-41.55 17.08-37.38Median 5.28 5.19 2.14 132.7 32.48 25.04Mean 5.46 6.08 2.14 140.2 31.08 27.38SD 0.99 2.72 0.46 36.23 5.75 6.75

Saar S1Güdingen1994-2009

Range 2.25-4.26 1.39-4.64 0.43-1.40 39.74-99.03 16.32-37.18 12.98-33.18Median 2.98 3.03 0.68 65.35 20.30 17.51Mean 2.98 3.13 0.81 69.69 21.43 19.07SD 0.66 0.99 0.31 17.30 5.22 6.28

S2Rehlingen1994-2009

Range 2.24-5.69 2.53-6.44 0.32-0.85 34.56-196.4 19.23-29.36 18.00-32.48Median 3.29 3.32 0.44 57.16 23.36 22.60Mean 3.48 3.63 0.49 70.68 23.25 22.84SD 0.88 1.06 0.17 42.55 3.08 3.97

Table S3: Metals and arsenic in muscle and liver of bream (Abramis brama) from the German ESB sampling sites.

Water Sampling site and period

Value Bream muscle Bream liverArsenicµg/g dw

Leadng/g dw

Mercuryng/g dw

Copperµg/g dw

Leadng/g dw

Cadmiumng/g dw

Copperµg/g dw

Zincµg/g dw

Lake Belau

B-Lake BelauMuscle: 1997-2011Liver:2003-2009

Range 0.11-0.67 0.50-53.58 106.0-225.8 0.98-1.48 42.26-131.8 113.3-364.5 59.56-128.2 118.3-179.2Median 0.19 28.20 153.78 1.25 46.53 155.8 81.38 124.3Mean 0.24 27.64 156.17 1.23 66.78 197.4 87.62 136.5SD 0.18 22.13 41.30 0.16 43.45 114.0 29.14 28.98

Danube D1- UImMuscle:2004-2011Liver:2004-2010

Range 0.26-0.47 5.13-27.05 322.2-529.5 1.08-1.40 37.08-80.28 228.7-538.0 52.03-104.8 113.2-157.0Median 0.32 16.88 435.4 1.23 62.50 271.3 90.38 132.5Mean 0.34 16.91 447.5 1.24 61.62 321.0 82.48 133.7SD 0.08 7.36 67.69 0.12 12.74 106.5 21.62 17.37

D2-KelheimMuscle:2004-2011Liver:2004-2010

Range 0.31-0.75 7.48-42.92 494.5-1295 1.14-1.26 98.90-169.2 204.8-884.5 81.48-213.2 120.8-201.0Median 0.61 33.60 714.3 1.22 132.8 323.7 123.3 144.2Mean 0.58 28.98 808.1 1.21 127.6 417.0 127.2 150.1SD 0.16 12.65 287.5 0.05 24.76 257.4 41.81 27.19

D3-JochensteinMuscle:2004-2011Liver:2004-2010

Range 0.46-0.92 16.88-73.32 1053-1530 1.10-1.77 111.9-274.0 1207-2183 79.35-159.3 109.7-175.8Median 0.52 28.64 1325 1.27 130.8 1382 108.2 141.5Mean 0.60 35.57 1332 1.36 151.8 1590 114.9 141.3SD 0.17 18.08 159.1 0.24 56.98 373.6 31.20 27.83

Table S3 (cont.): Metals and arsenic in muscle and liver of bream (Abramis brama) from the German ESB sampling sites.

Water Sampling site and period

Value Bream muscle Bream liverArsenicµg/g dw

Lead ng/g dw

Mercuryng/g dw

Copperµg/g dw

Leadng/g dw

Cadmiumng/g dw

Copperµg/g dw

Zincµg/g dw

Elbe E1-ProssenMuscle:1993-2011Liver:2002-2010

Range 0.20-0.47 44.60-178.5 824.2-2859 1.08-1.72 142.0-467.0 715.8-3140 61.20-145.3 109.6-172.6Median 0.34 90.48 1592 1.36 310.2 2102 75.68 117.8Mean 0.34 95.56 1658 1.37 303.7 1925 86.67 128.1SD 0.07 36.45 562.5 0.16 106.7 912.4 25.64 22.09

E2-ZehrenMuscle:1993-2011Liver:2002-2010

Range 0.10-0.64 42.24-172.4 958.1-3376 1.21-1.98 258.5-541.3 2352-9070 92.13-157.2 120.0-163.8Median 0.42 104.2 2033 1.38 372.8 5650 126.5 150.2Mean 0.44 112.3 2050 1.44 376.4 5512 126.4 146.7SD 0.13 36.24 601.7 0.19 108.8 1887 23.68 16.60

E3-BarbyMuscle:1993-2011Liver:2002-2010

Range 0.29-0.64 51.36-167.9 1050-4196 1.21-2.46 259.5-542.3 1093-8888 78.37-193.5 134.8-186.7Median 0.40 85.86 1540 1.48 363.2 4640 136.8 169.5Mean 0.42 93.59 1902 1.62 382.1 4875 134.7 158.7SD 0.10 33.47 881.1 0.40 83.42 2330 41.91 19.83

E4-CumlosenMuscle:1993-2011Liver:2002-2010

Range 0.21-0.83 36.44-164.0 1041-3286 1.47-4.55 161.8-303.8 2355-7564 61.37-112.7 108.2-156.5Median 0.31 70.88 1492 2.38 263.00 4068 92.85 140.5Mean 0.34 78.92 1782 2.51 259.6 4249 90.74 137.2SD 0.14 33.77 713.9 0.78 44.43 1647 16.74 16.81

E5BlankeneseMuscle:1993-2011Liver:2002-2010

Range 0.38-0.76 7.86-158.8 351.2-1650 1.28-3.81 74.05-131.8 74.27-249.2 17.93-51.05 64.23-113.5Median 0.52 57.88 577.7 2.04 86.22 133.3 19.67 76.13Mean 0.53 60.18 882.8 2.28 94.86 143.6 25.16 82.04SD 0.10 38.72 469.1 0.88 18.97 52.69 11.22 14.83

Table S3 (cont.): Metals and arsenic in muscle and liver of bream (Abramis brama) from the German ESB sampling sites.

Water Sampling site and period

Value Bream muscle Bream liverArsenicµg/g dw

Lead ng/g dw

Mercuryng/g dw

Copperµg/g dw

Leadng/g dw

Cadmiumng/g dw

Copperµg/g dw

Zincµg/g dw

Mulde MU-DessauMuscle:1995-2011Liver: 2002-2010

Range 0.24-0.49 35.72-160.0 916.2-4127 1.54-3.51 198.8-499.2 9440-23167 78.07-144.7 115.7-177.5Median 0.38 72.24 1363 2.36 282.7 12417 111.0 138.5Mean 0.37 78.47 1779 2.33 312.1 13050 110.0 140.3SD 0.06 34.02 992.6 0.62 99.30 3953 20.12 19.24

Saale SA-WettinMuscle:1995-2011Liver: 2002-2010

Range 0.16-0.72 40.48-151.2 942.7-1962 0.85-1.50 193.6-718.7 304.2-753.0 96.03-143.2 116.8-171.8Median 0.36 83.75 1552 1.22 308.6 530.7 118.5 128.8Mean 0.42 87.43 1494 1.22 349.4 502.2 118.9 139.6SD 0.19 34.49 293.8 0.19 159.9 143.0 17.41 20.77

Table S3 (cont.): Metals and arsenic in muscle and liver of bream (Abramis brama) from the German ESB sampling sites.

Water Sampling site and period

Value Bream muscle Bream liverArsenicµg/g dw

Leadng/g dw

Mercuryng/g dw

Copperµg/g dw

Leadng/g dw

Cadmiumng/g dw

Copperµg/g dw

Zincµg/g dw

Rhine R1-WeilMuscle:1995-2011Liver: 2002-2010

Range 0.24-0.54 15.82-78.29 364.2-916.3 1.03-2.19 51.08-120.2 42.83-204.4 15.65-60.73 55.50-83.73Median 0.42 32.83 697.9 1.51 59.60 138.4 32.43 68.23Mean 0.40 41.66 689.3 1.50 76.43 130.0 33.96 67.80SD 0.09 21.88 162.2 0.26 27.40 53.98 12.27 10.62

R2-IffezheimMuscle:1995-2011Liver: 2002-2010

Range 0.39-0.79 15.85-268.0 688.3-1429 1.02-1.64 164.8-275.0 587.4-1183 81.37-102.17 109.3-129.8Median 0.56 58.62 1023 1.31 186.8 851.2 88.50 124.0Mean 0.58 75.02 1037 1.28 196.3 892.1 91.30 123.5SD 0.12 61.05 164.7 0.20 35.01 215.1 6.96 6.17

R3-KoblenzMuscle:1995-2011Liver: 2002-2010

Range 0.32-0.68 27.08-118.5 366.5-878.4 0.93-1.31 100.4-199.3 145.3-1466 40.43-95.62 68.38-107.7Median 0.44 67.20 483.3 1.16 157.4 408.0 62.67 92.15Mean 0.47 65.26 527.1 1.14 150.9 526.0 65.11 91.04SD 0.11 27.34 156.3 0.12 29.10 452.1 16.97 12.48

R4-BimmenMuscle:1995-2011Liver: 2002-2010

Range 0.43-0.97 61.86-186.2 560.6-1945 1.00-1.61 137.2-389.8 602.3-3104 52.67-133.7 88.82-145.7Median 0.64 82.89 895.0 1.23 282.50 2352 96.92 123.0Mean 0.69 104.45 984.5 1.23 274.02 2074 99.49 120.4SD 0.18 41.55 349.1 0.19 90.43 1035 29.70 22.34

Saar S1-GüdingenMuscle:1994-2011Liver: 2002-2010

Range 0.15-0.56 35.83-255.7 315.5-548.6 1.15-1.67 96.26-170.83 108.8-238.5 34.93-77.50 68.95-114.3Median 0.24 74.46 439.1 1.42 132.7 170.5 44.82 94.40Mean 0.28 85.43 435.4 1.41 131.3 175.6 49.79 95.43SD 0.11 51.27 59.50 0.12 24.55 42.11 14.68 13.25

S2-RehlingenMuscle:1994-2011Liver: 2002-2010

Range 0.30-0.76 30.30-122.2 397.5-633.0 1.04-1.65 119.0-187.2 86.78-230.0 91.22-155.0 111.3-156.5Median 0.51 51.67 521.4 1.26 158.3 166.2 114.6 129.3Mean 0.52 64.84 524.7 1.24 155.3 169.4 119.0 133.9SD 0.15 29.25 65.42 0.14 19.77 50.69 18.51 13.97

Table S4: Time trend analysis of arsenic and metals in suspended particulate matter (SPM) from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%. Time span: 2005 – 2009 (5 years). Exception: Saar: 2006 – 2009 (4 years)

Water Sampling site

Parameters SPMArsenic Lead Cadmium Mercury Copper Nickel Zinc

Elbe E1

Prossen

Yearly trend 9.7% n.s. 6.9% n.s. 10% n.s. 5.7% n.s. 12% n.s. 12% n.s. 8.3% n.s.95%-CI -7.5; 30 -14; 32 -11; 37 -23; 45 -5.0; 31 -11; 40 -8.8; 28r² 0.50 0.25 0.41 0.09 0.61 0.44 0.42p <0.182 <0.397 <0.244 <0.616 <0.117 <0.222 <0.236

E2

Zehren

Yearly trend 1.4% n.s. 7.5% n.s. 16% n.s. 6.2% n.s. 10% n.s. 17% n.s. 15% n.s.95%-CI -26; 39 -27; 58 -37; 118 -48; 116 -30; 73 -27; 90 -29; 86r² 0.01 0.10 0.17 0.02 0.15 0.28 0.21p <0.862 <0.599 <0.497 <0.790 <0.529 <0.359 <0.327

E3

Barby

Yearly trend -11% n.s. -2.2% n.s. -1.5% n.s. -11% n.s. -4.7% n.s. -2.2% n.s. -5.1% n.s.95%-CI -28; 9.9 -14; 12 -23; 26 -19; -2.1 -9.4; 0.3 -15; 13 -18; 10r² 0.51 0.09 0.01 0.83 0.75 0.08 0.30p <0.174 <0.616 <0.831 <0.033 <0.061 <0.649 <0.344

E4

Cumlosen

Yearly trend -3.1% n.s. 0.7% n.s. 2.6% n.s. -4.4% n.s. -2.4% n.s. 4.4% n.s. 0.7% n.s.95%-CI -12; 6.3 -14; 17 -41; 77 -15; 7.0 -13; 9.6 -17; 31 -16; 22r² 0.29 0.01 0.01 0.35 0.12 0.10 0.00p <0.353 <0.870 <0.861 <0.296 <0.562 <0.597 <0.879

E5

Blankenese

Yearly trend 1.5% n.s. 5.7% n.s. 27% n.s. 1.5% n.s. 4.4% n.s. 6.3% n.s. 5.8% n.s.95%-CI -3.8; 7.0 -3.2; 15 -63; 331 -8.2; 13 -0.9; 10 1.1; 12 -7.7;21r² 0.20 0.57 0.11 0.07 0.70 0.83 0.36p <0.454 <0.142 <0.586 <0.661 <0.080 0.033 <0.281

Table S4 (cont.): Time trend analysis of arsenic and metals in suspended particulate matter (SPM) from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%. Time span: 2005 – 2009 (5 years). Exception: Saar: 2006 – 2009 (4 years)

Water Sampling site

Parameters SPMArsenic Lead Cadmium Mercury Copper Nickel Zinc

Saale SA

Wettin

Yearly trend -4.5% n.s. -1.9.0% n.s. 12% n.s. -13% n.s. -3.4% n.s. 0.30% -0.8% n.s.95%-CI -23; 19 -13; 11 -; 246 -27; 4.2 -15; 9.9 -15; 19 -21; 23r² 0.14 0.08 0.03 0.67 0.20 0.00 0.00p <0.545 <0.650 <0.758 <0.092 <0.457 <0.911 <0.877

Mulde Mu

Dessau

Yearly trend 3.7% n.s. 1.1% n.s. 7.7% n.s. 5.2% n.s. 4.3% n.s. 13% increase 17% n.s.95%-CI -5.1; 13 -6.9; 9.3 1.7; 14 -10; 23 -0.2; 9.0 7.9; 18 -18; 67r² 0.38% 0.06 0.85 0.26 0.75 0.96 0.39p <0.271 <0.678 <0.029 <0.384 <0.059 <0.007 <0.260

Rhine R1

Weil

Yearly trend -0.5% n.s. 2.1% n.s. 12% n.s. 2.6% n.s. -0.02% n.s. 6.4% n.s. 4.4% n.s.95%-CI -9; 9.3 -10; 16 -34; 88 -29; 49 -8.1; 8.9 -9.0; 24 -1.1; 10r² 0.01 0.08 0.12 0.02 0.00 0.35 0.68p <0.844 <0.647 <0.574 <0.816 <0.942 <0.295 <0.087

R2

Iffezheim

Yearly trend -3.2% n.s. 2.2% n.s. 7.4% n.s. -2.4% n.s. -1.6% n.s. 3.5% n.s. 2.4% n.s.95%-CI -8.2; 2.0 -6.2; 12 -16; 39 -12; 8.7 -6.0; 3.0 -12; 22 -0.20; 5.1r² 0.57 0.18 0.21 0.15 0.29 0.12 0.74p <0.142 <0.482 <0.445 <0.523 <0.353 <0.564 <0.063

R3

Koblenz

Yearly trend 3.1% n.s. 3.4% n.s. 14% n.s. -3.9% n.s. 0.2% n.s. 8.0% n.s. 5.0% n.s.95%-CI -5.6; 13 -7.6; 16 -18; 60 -12; 5.0 -10; 12 -2.4; 20 -2.0; 13r² 0.29 0.23 0.34 0.40 0.00 0.66 0.63p <0.353 <0.414 <0.299 <0.249 <0.909 <0.096 <0.110

R4

Bimmen

Yearly trend -1.0% n.s. -1.3% n.s. 1.7% n.s. -8.9% n.s. -3.4% n.s. 2.1% n.s. 7.3% n.s.95%-CI -3.8; 1.9 -9.0; 7.1 -34; 58 -18; 1.6 -11; 4.8 -12; 18 -25; 54r² 0.28 0.08 0.00 0.71 0.38 0.06 0.11p <0.365 <0.654 <0.877 <0.075 <0.270 <0.683 <0.581

Table S4 (cont.): Time trend analysis of arsenic and metals in suspended particulate matter (SPM) from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%. Time span: 2005 – 2009 (5 years). Exception: Saar: 2006 – 2009 (4 years)

Water Sampling site

Parameters SPMArsenic Lead Cadmium Mercury Copper Nickel Zinc

Saar S1

Güdingen

Yearly trend -2.9% n.s. -2.1% n.s. -14% n.s. -18% decrease -7.2% n.s. 6.6% n.s. 1.0% n.s.95%-CI -27; 31 -27; 31 -34; 10 -47; 28 -29; 21 -16; 36 -27; 40r² 0.08 0.05 0.77 0.64

/Kendall’s tau :***/SD(sm): 0.00

0.42 0.39 0.01

p <0.704 <0.770 <0.128 <0.200 /p<0.042 (tau) (p<0.001 (SD(sm))

<0.353 <0.377 <0.877

S2

Rehlingen

Yearly trend -5.3% n.s. 2.9% n.s. -16% n.s. -1.9% n.s. -7.0% n.s. 8.2% increase -1.9% n.s.95%-CI -23; 16 -20; 31 -52; 48 -18; 17 -22; 10 -0.4; 17 -39; 58r² 0.39 0.12 0.47 0.09 0.62 0.89(Kendall’s

tau: 1.00/SD(sm): 0.00

0.01

p <0.380 <0.656 <0.319 <0.694 <0.215 <0.062 / p<0.042 (tau) / p<0.001 (SD(sm))

<0.850

Table S5: Time trend analysis of arsenic and metals in zebra mussels from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Zebra musselArsenic Lead Cadmium Mercury Copper Nickel

Lake Belau B Period 1997-2009 1999-2009 1997-2009 1997-2009 1997-2009 1997-2009No of values 7 6 7 7 7 7Yearly trend -0.3% n.s. -15% n.s. -7.4% decrease -5.2% n.s. -7.7% decrease -6.2% decrease95%-CI 2.6; 1.9 -25; -3.3 -12; -2.3 -10; 0.4 -10; -4.9 -11; -1.2r² 0.03 0.75 0.73 0.53 0.90 0.67p <0.702 <0.026 0.015 <0.061 <0.001 <0.025

Danube D1

Ulm

Period 2003-2009 2003-2009 2003-2009 2003-2009 2003-2009 2003-2009No of values 7 7 7 7 7 7Yearly trend -2.7% n.s. 8.0% n.s. -3.4% n.s. 4.1% n.s. 2.3% n.s. 5.3% n.s.95%-CI -7.6; 2.6 -3.6; 21 -8.9; 2.4 -3.1; 12 -4.3; 9.5 -8.5; 21r² 0.25 0.38 0.32 0.29 0.14 0.15p <0.249 <0.141 <0.187 <0.208 <0.420 <0.391

D2

Kelheim

Period 2004-2009 2004-2009 2004-2009 2004-2009 2004-2009 2004-2009No of values 6 6 6 6 6 6Yearly trend -4.0% n.s. 12% increase 3.3% n.s. 12% n.s. 21% increase 16% increase95%-CI -14; 6.9 4.8; 20 -20; 34 -11; 40 17; 23 5.1; 30r² 0.22 0.85 0.03 0.30 0.99 0.81p <0.352 <0.010 <0.739 <0.262 <0.001 <0.016

D3

Jochenstein

Period 2004-2009 2004-2009 2004-2009 2004-2009 2004-2009 2004-2009No of values 5 5 5 5 5 5Yearly trend -0.8% n.s. 2.4% n.s. -0.3 n.s. 0.9% n.s. 18% n.s. 7.7% n.s.95%-CI -9; 9.1 -16; 23 -9.4; 9.6 -5.2; 7.5 -2.6; 45 -0.8; 17.4r² 0.03 0.05 0.00 0.07 0.72 0.74p <0.785 <0.706 <0.879 <0.664 <0.072 <0.065

Table S5 (cont.): Time trend analysis of arsenic and metals in zebra mussels from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Zebra musselArsenic Lead Cadmium Mercury Copper Nickel

Elbe E1

Prossen

Period 1999-2009 1999-2009 1999-2009 1999-2009 1999-2009 1999-2009No of values 11 11 11 11 11 11Yearly trend 0.9% n.s. 0.8% n.s. 2.3% n.s. -5.2% n.s. -0.8% n.s. -1.6% n.s.95%-CI -2.3; 4.2 -5.2; 7.1 -5.9; 12 -11; 1.0 -3.4; 1.8 -4.9; 1.8r² 0.04 0.01 0.04 0.28 0.05 0.11p <0.558 <0.767 <0.563 <0.089 <0.498 <0.310

E2

Zehren

Period 2000-2009 2000-2009 2000-2009 2000-2009 2000-2009 2000-2009No of values 10 10 10 10 10 10Yearly trend 1.1% n.s. 20% increase -18% n.s. 0.3% n.s. -0.4% n.s. 5.5% n.s.95%-CI -5.3; 7.8 6.3; 30 -35; -4.3 -4.6; 5.4 -5.4; 5.0 -4.4; 16r² 0.02 0.60 0.52 0.00 0.00 0.16p <0.711 <0.008 <0.018 <0.855 <0.852 <0.244

E3

Barby

Period 1998-2009 1998-2009 1998-2009 1998-2009 1998-2009 1998-2009No of values 12 12 12 12 12 12Yearly trend -0.5% n.s. 7.8% n.s. 3.7% n.s. -7.6% decrease 2.0% n.s. -0.8% n.s.95%-CI -3.8; 2.8 -4.3; 21 -2.4; 10 -11; -3.5 -1.2; 5.3 -5.2; 3.7r² 0.01 0.17 0.15 0.63 0.17 0.02p <0.726 <0.187 <0.207 <0.002 <0.184 <0.687

E4

Cumlosen

Period 1998-2009 1998-2009 1998-2009 1998-2009 1998-2009 1998-2009No of values 10 10 10 10 10 10Yearly trend -0.5% n.s. -1.9% n.s. 5.0% n.s. -3.4% n.s. 0.4% n.s. -1.2% n.s.95%-CI -4.4; 3.7 -9; 6.7 -3.6; 14 -8.6; 2.1 -1.4; 2.2 -7.2; 5.1r² 0.01 0.03 0.18 0.21 0.04 0.03p <0.787 <0.623 <0.223 <0.184 <0.609 <0.661

Table S5 (cont.): Time trend analysis of arsenic and metals in zebra mussels from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Zebra musselArsenic Lead Cadmium Mercury Copper Nickel

Elbe E5

Blankenese

Period 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009No of values 13 12 13 13 13 13Yearly trend -0.1% n.s. 2.2% n.s. -2.3% n.s. -1.8% n.s. 3.0% increase 5.3% increase95%-CI -2.7; 2.4 -1.4; 6.0 -5.6; 1.2 -4.2; 0.7 1.2; 4.8 2.2; 8.5r² 0.00 0.15 0.16 0.19 0.55 0.57p <0.871 <0.206 <0.166 <0.137 <0.004 <0.003

Rhine R1

Weil

Period 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009No of values 6 5 6 6 6 6Yearly trend -2.9% n.s. 2.5% n.s. -2.8% decrease 6.0% n.s. 1.1% n.s. 1.5% n.s.95%-CI -7.2; 1.7 -16; 26 -6.8; 1.4 -4.2; 17 -5.6; 8.2 -5.6; 9.2r² 0.44 0.05 0.47 / Kendall’s

tau: -0.730.39 0.04 0.07

p <0.149 <0.716 <0.133 (p<0.039 (tau))

<0.186 <0.688 <0.607

R2

Iffezheim

Period 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009No of values 4 4 4 4 4 4Yearly trend n.d. n.d. n.d. n.d. n.d. n.d.95%-CI n.d. n.d. n.d. n.d. n.d. n.d.r² n.d. n.d. n.d. n.d. n.d. n.d.p n.d. n.d. n.d. n.d. n.d. n.d.

R3

Koblenz

Period 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009No of values 9 8 9 9 9 9Yearly trend -1.1% n.s. -1.0% n.s. -4.2% decrease -3.1% n.s. -2.7% n.s. -6.8% decrease95%-CI -3.8; 1.8 -10; 9.0 -9.1; 0.9 -7.9; 2.0 -5.8; 0.6 -10; -2.8r² 0.10 0.01 0.35/ Kendall’s

tau: -0.560.23 0.35 0.69

p <0.411 <0.789 <0.091 / p<0.037 (tau)

<0.188 <0.090 <0.006

Table S5 (cont.): Time trend analysis of arsenic and metals in zebra mussels from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Zebra musselArsenic Lead Cadmium Mercury Copper Nickel

R4

Bimmen

Period 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009 1995-2009No of values 10 9 10 10 10 10Yearly trend -1.8% 6.4% increase 1% n.s. 2.4% n.s. -0.8% n.s. -0.1% n.s.95%-CI -3.9; 0.40 1.3; 12 -2.4; 4.5 -1.9; 6.8 -3.5; 2.0 -4.0; 4.0r² 0.31 0.56 0.05 0.17 0.05 0.00p <0.093 <0.020 <0.521 <0.231 <0.533 <0.915

Saar S1

Güdingen

Period 1994-2009 1994-2009 1994-2009 1994-2009 1994-2009 1994-2009No of values 15 15 15 15 15 15Yearly trend -0.7% n.s. 1.9% n.s. 4.9% increase -1.6% n.s. 2.5% increase 2.6% n.s.95%-CI -3.1; 1.9 -2.4; 6.4 1.1; 8.9 -4.5; 1.4 0.3; 4.8 -0.9; 6.3r² 0.02 0.07 0.38 0.09 0.32 0.17p <0.599 <0.353 <0.014 <0.278 <0.026 <0.127

Rehlingen Period 1994-2009 1994-2009 1994-2009 1994-2009 1994-2009 1994-2009No of values 16 15 16 16 16 16Yearly trend -3.0% decrease -0.1% n.s. 2.6% n.s. -6.8% decrease 0.30% n.s. -0.2% n.s.95%-CI -5.3; -0.6 -3.3; 3.1 -0.8; 6.2 -10; -2.8 -1.2; 1.9 -2.3; 1.8r² 0.33 0.00 0.16 0.47 0.01 0.01p <0.019 <0.883 <0.126 <0.003 0.684 <0.781

Table S6: Time trend analysis of arsenic and metals in bream from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Bream muscle Bream liverArsenic Lead Copper Mercury Lead Cadmium Copper Zinc

Lake Belau

B period 1997-2009 1997-2009 1997-2009 1997-2009 2003-2009 2003-2009 2003-2009 2003-2009No of values 8 7 8 8 4 4 4 4Yearly trend 0.4% n.s. -20% n.s. 1.1% n.s. -3.8%

decrease-5.4% n.s. 17% n.s. -11% decrease -6.5% n.s.

95%-CI -10;13 -39; 3.3 -1.4; 3.7 -7.3; -0.3 -49; 75 -15; 63 -18; -3.6 -16; 4.4r² 0.0 0.5 0.16 0.54 0.07 0.70 0.95 0.77p <0.901 <0.073 <0.331 <0.037 <0.731 <0.166 <0.034 <0.125

Danube D1

Ulm

period 2004-2011 2004-2011 2004-2011 2004-2011 2004-2010 2004-2010 2004-2010 2004-2010No of values 8 8 8 8 7 7 7 7Yearly trend -2.3% n.s. -0.3% n.s. 0.6% n.s. -1.9% n.s. 6.5% n.s. -3.8% n.s. -8.4% n.s. -4.0% n.s.

95%-CI -10; 6.4 -20; 25 -3.2; 4.5 -7.9; 4.4 -3.7; 17 -17; 12 -18; 2.2 -8.7; 1.0r² 0.07 0.00 0.02 0.09 0.34 0.08 0.46 0.47p <0.539 <0.923 <0.721 <0.483 <0.168 <0.534 <0.092 <0.09

D2

Kelheim

period 2004-2011 2004-2011 2004-2011 2004-2011 2004-2010 2004-2010 2004-2010 2004-2010No of values 8 7 8 8 7 7 7 7Yearly trend -3.4% n.s. -2.5% n.s. 0.8% n.s. 10% n.s. 3.0% n.s. 13% n.s. 12% n.s. 3.9% n.s.

95%-CI -15; 8.9 -27; 31 -0.6; 2.2 -0.8; 22 -6.5; 14 -14; 46 0.5; 23 -4.1; 13r² 0.08 0.01 0.26 0.46 0.11 0.20 0.59 0.23p <0.508 <0.817 <0.199 <0.063 <0.467 <0.385 <0.043 <0.277

D3

Jochen-stein

Period 2004-2011 2004-2011 2004-2011 2004-2011 2004-2010 2004-2010 2004-2010 2004-2010No of values 8 8 8 8 7 7 7 7Yearly trend -7.6% n.s. 9.6% n.s. 4.9% n.s. 1.0% n.s. 6.8% n.s. 5.7% n.s. 4.9% n.s. 3.7% n.s.

95%-CI -14; -0.9 -6.9; 30 -0; 10 -3.8; 6.1 -7.8; 23 -4.6; 17 -8.4; 20 -6.0; 14r² 0.56 0.24 0.50 0.04 0.21 0.28 0.14 0.15p <0.032 <0.216 <0.050 <0.645 <0.302 <0.222 <0.413 <0.395

Table S6 (cont.): Time trend analysis of arsenic and metals in bream from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Bream muscle Bream liverArsenic Lead Copper Mercury Lead Cadmium Copper Zinc

Elbe E1

Prossen

Period 1993-2011 1993-2011 1993-2011 1993-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 19 18 19 19 9 9 9 9Yearly trend 0.8% n.s. -3.1% n.s. -1.7%

decrease-5.3% decrease

-11% n.s. -13% n.s. -2.0% n.s. -4.6% decrease

95%-CI -1.1; 2.7 -6.2; 0.1 -2.3; -1.0 -6.6; -3.8 -16; -5.2 -24; 0.6 -9.5; 6.7 -7.5; -1.5r² 0.05 0.21 0.63 0.78 0.72 0.42 0.04 0.64p <0.375 <0.055 <0.001 <0.001 <0.004 <0.056 <0.605 <0.01

E2

Zehren

Period 1993-2011 1993-2011 1993-2011 1993-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 19 18 19 19 9 9 9 9Yearly trend 4.2%

increase-3.0% n.s. -1.3%

decrease-4.8% decrease

-6.6% n.s. -10% decrease

-4.2% n.s. -3.7% decrease

95%-CI 1.1; 7.4 -5,9; 0.0 -2.2; -0.3 -6.0; -3.5 -13; 0.4 -17; -3.2 -8.9; 1.0 -5.4; -1.9r² 0.33 0.22 0.32 0.79 0.41 0.62 0.34 0.76p <0.01 <0.049 <0.011 <0.001 <0.06 <0.011 <0.095 0.002

E3

Barby

Period 1993-2011 1993-2011 1993-2011 1993-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 19 18 19 19 9 9 9 9Yearly trend -0.5% n.s. -1.0% n.s. -3.6%

decrease-5.0% decrease

5.2% n.s. 14% n.s. 5.3% n.s. 1.7% n.s.

95%-CI -2.5; 1.4 -4.2; 2.2 -4.6; -2.6 -7.4; -2.6 -0.3; 10 -4.2; 35 -4.1; 16 -2.2; 5.7r² 0.02 0.03 0.76 0.51 0.42 0.31 0.20 0.13p <0.569 <0.508 <0.001 <0.001 <0.059 <0.119 <0.228 <0.344

E4

Cumlosen

Period 1993-2011 1993-2011 1993-2011 1993-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 19 18 19 19 9 9 9 9Yearly trend 2.5% n.s. -4.5%

decrease-4.6% decrease

-3.6% decrease

0.5% n.s. 0.2% n.s. -1.4% n.s. -0.4 n.s.

95%-CI -0.1; 5.3 -7.4; -1.6 -5.7; -3.5 -6.3; -0.9 -6.7; 6.0 -11; 14 -7.5; 5.1 -4.4; 3.8r² 0.19 0.39 0.82 0.32 0.01 0.0 0.04 0.01p <0.058 <0.005 <0.001 <0.011 <0.830 <0.918 <0.620 <0.813

Table S6 (cont.): Time trend analysis of arsenic and metals in bream from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Bream muscle Bream liverArsenic Lead Copper Mercury Lead Cadmium Copper Zinc

Elbe E5

Blanke-nese

Period 1993-2011 1993-2011 1993-2011 1993-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 19 18 19 19 9 9 9 9Yearly trend 0.3% n.s. -9.3%

decrease-6.0% decrease

-8,4% decrease

0.8% n.s. -5,9% n.s. 4.3% n.s. 1.6% n.s.

95%-CI -1.4; 1.9 -14;-4.7 -7.4; -4.6 -10; -6,7 -6.7; 5.4 -16; 4.8 -6,9; 16 -3.6; 7.3r² 0.01 0.52 0.81 0.85 0.01 0.20 0.10 0.07p <0.754 <0.001 <0.001 <0.001 <0.751 <0.224 <0.415 <0.495

Saale SA

Wettin

Period 1995-2011 1995-2011 1995-2011 1995-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 17 16 17 17 9 9 9 9Yearly trend 9.1%

increase0.9% n.s. -1.9%

decrease2.9% increase -12% decrease 5.3% n.s. -0.7% n.s. -1.3% n.s.

95%-CI 6.5; 12 -3.6; 5.7 -3.2; -0.6 1.1; 4.7 -18; -5.8 -3.0; 14 -5.4; 4.1 -5.8; 3.4r² 0.79 0.01 0.39 0.44 0.74 0.25 0.02 0.06p <0.001 <0.684 <0.007 <0.004 <0.003 <0.173 <0.727 <0.517

Mulde MU

Dessau

Period 1995-2011 1995-2011 1995-2011 1995-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 17 16 17 17 9 9 9 9Yearly trend 0.3% n.s. -4.8%

decrease-3.7% decrease

-8.1% decrease

1.6% n.s. 3.3% n.s. 1.2% n.s. -0.3% n.s.

95%-CI -1.6; 2.3 -8.4; -1.0 -5.6; -1.7 -10; -5.6 -7.8; 12 -4.2; 12 -4.8; 7.6 -4.5; 4.2r² 0.01 0.34 0.51 0.76 0.02 0.13 0.03 0.0p <0.718 <0.017 <0.001 <0.001 <0.709 <0.345 <0.662 <0.857

Table S6 (cont.): Time trend analysis of arsenic and metals in bream from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Bream muscle Bream liverArsenic Lead Copper Mercury Lead Cadmium Copper Zinc

Rhine R1

Weil

Period 1995-2011 1995-2011 1995-2011 1995-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 16 15 16 16 9 9 9 9Yearly trend 3.5%

increase-5.7% decrease

0.3% n.s. -3.3% decrease

0.7% n.s. -1.8% n.s. 7.5% n.s. 2.6% n.s.

95%-CI 1.3; 5.5 -11; -0.2 -1.7; 2.3 -5.6; -1.1 -11; 12 -17; 16 -2.8; 18 -1.9; 7.5r² 0.47 0.28 0.01 0.41 0.0 0.01 0.29 0.21p <0.003 <0.04 <0.741 <0.007 <0.861. <0.795 <0.131 <0.215

R2

Iffezheim

Period 1995-2011 1995-2011 1995-2011 1995-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 17 16 17 17 9 9 9 9Yearly trend 2.0% n.s. -4.8% n.s. -0.6% n.s. -1.3% n.s. -2.4% n.s. -1.0% n.s. -0.5% n.s. -0.8% n.s.

95%-CI 0.0; 4.2 -11; 2.5 -2.3; 1.0 -2.9; 0.3 -7.0; 2.4 -8.6; 7.3 -2.9; 1.9 -2.4; 0.7r² 0.22 0.12 0.04 0.17 0.17 0.01 0.03 0.20p <0.052 <0.177 <0.419 <0.095 <0.277 <0.770 <0.648 <0.220

R3

Koblenz

Period 1995-2011 1995-2011 1995-2011 1995-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 17 16 17 17 9 9 9 9Yearly trend 2.5% n.s. -6.0%

decrease-0.9% n.s. -0.9% n.s. 1.6% n.s. 30%

increase4.8% n.s. 2.8% n.s.

95%-CI 0.6; 4.6 -9.5; -2.1 -1.9; 0.2 -3.7; 1.9 -4.7; 8.4 18; 42 -2.8; 13 -1.2; 7,0r² 0.33 0.43 0.17 0.03 0.05 0.87 0.24 0.28p <0.015 <0.005 <0.096 <0.498 <0.574 <0.001 <0.178 <0.144

R4

Bimmen

Period 1995-2011 1995-2011 1995-2011 1995-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 17 16 17 17 9 9 9 9Yearly trend 4.0%

increase-6.6% decrease

-1.6% decrease

-4.0% decrease

-2.8% n.s. -4.3% n.s. -1.3% n.s. -0.8% n.s.

95%-CI 2.1; 6.0 -8.5; -4.5 -3.0; -0.2 -6.7; -1.4 -13; 9.3 -22; 17 -11; 9.7 -6.9; 5.7r² 0.59 0.76 0.30 0.41 0.04 0.04 0.01 0.01p <0.001 <0.001 <0.023 <0.005 <0.591 <0.627 <0.771 0.758

Table S6 (cont.): Time trend analysis of arsenic and metals in bream from the German ESB sites using the PIA programme (Bignert 2007), alpha 5%; power 80%

Water Sampling site

Parameters Bream muscle Bream liverArsenic Lead Copper Mercury Lead Cadmium Copper Zinc

Saar S1

Güdingen

Period 1994-2011 1994-2011 1994-2011 1994-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 18 17 18 18 9 9 9 9Yearly trend 5.5%

increase-6.3% decrease

-0.8% n.s. 0.3% n.s. -2.3% n.s. 6.6% n.s. 3.9% n.s. 2.0% n.s.

95%-CI 3.1; 8.0 -9.5; -2.6 -1.5; 0.0 -1.1; 1.6 -7.8; 3.7 0.6; 13 -4.8; 13 -2.5; 6.6r² 0.60 0.46 0.21 0.01 0.11 0.49 0.13 0.13p <0.001 <0.003 <0.055 <0.684 <0.392 <0.035 <0.342 <0.337

S2

Rehlingen

Period 1994-2011 1994-2011 1994-2011 1994-2011 2002-2010 2002-2010 2002-2010 2002-2010No of values 18 17 18 18 9 9 9 9Yearly trend 3.4%

increase-5.9 decrease

-1.0% n.s. 0.3% n.s. 2.8% n.s. 9.7% increase

1.5% n.s. 1.1% n.s.

95%-CI 1.1; 5.8 -8.8; -3.1 -2.0; -0.1 -1.0; 1.6 -0.7; 6.5 2.5; 17 -3.3; 6.5 -2.2; 4.4r² 0.37 0.55 0.24 0.01 0.34 0.60 0.07 0.08p <0.007 <0.001 <0.037 <0.641 <0.095 <0.015 <0.501 <0.460