<table><caption>**Table IV.** Values of PAFi above the Th5% (representative of a potential ecological risk) for each effect, life stage, year and river studied when using unquantified and quantified environmental data. Substances above the Th5% using only quantified environmental data are shown in bold. In dark gray, values about embryos and in light gray, larvae. As a reminder, PAFi represents the average annual individual PAF specific to each chemical compound and each life stage of the fish taxon for each effect tested in each spawning ground.</caption><thead><tr><th>Chemicals (Categories)</th><th>Rivers</th><th>Life stages</th><th>2006</th><th>2007</th><th>2008</th><th>2009</th><th>2010</th><th>2011</th><th>2012</th><th>2013</th><th>2014</th><th>2015</th><th>2016</th><th>2017</th><th>2018</th><th>2019</th><th>2020</th><th>2021</th></tr></thead><tbody><tr><td colspan="20"><strong>Development</strong></td></tr><tr><td>Estrone (HCPs)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>33</td><td></td><td></td></tr><tr><td>Estrone (HCPs)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>41</td><td>41</td><td>41</td></tr><tr><td>Calcium (Metals)</td><td>D</td><td>larva</td><td>18</td><td>13</td><td>14</td><td>14</td><td>13</td><td>16</td><td>15</td><td>13</td><td>11</td><td>12</td><td>14</td><td>14</td><td>12</td><td>14</td><td>15</td><td>10</td></tr><tr><td>Calcium (Metals)</td><td>G</td><td>larva</td><td>23</td><td>29</td><td>27</td><td>27</td><td>23</td><td>23</td><td>22</td><td>27</td><td>27</td><td>26</td><td>25</td><td>24</td><td>25</td><td>23</td><td>23</td><td>28</td></tr><tr><td>Copper (Metals)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td>9</td><td></td><td></td><td>6</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Copper (Metals)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td></td><td>5</td><td>14</td><td></td><td>7</td><td></td><td></td><td>9</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Zinc (Metals)</td><td>G</td><td>larva</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>6</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Tributylstannane (OIPs)</td><td>D</td><td>embryon</td><td></td><td>9</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Bisphenol A (OIPs)</td><td>D</td><td>larva</td><td></td><td></td><td></td><td>7</td><td></td><td></td><td></td><td>798</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Bisphenol A (OIPs)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>9</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Dioctyl phthalate (OIPs)</td><td>D</td><td>larva</td><td></td><td>57</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Benzolalpyrene (PAHs)</td><td>D</td><td>embryon</td><td></td><td>6</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan="20"><strong>Behavior</strong></td></tr><tr><td>Estrone (HCPs)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>30</td><td></td><td></td></tr><tr><td>Estrone (HCPs)</td><td>D</td><td>larva</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>30</td><td></td><td></td></tr><tr><td>Estrone (HCPs)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>37</td><td>37</td><td>37</td></tr><tr><td>Estrone (HCPs)</td><td>G</td><td>larva</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>37</td><td>37</td><td>37</td></tr><tr><td>4-tert-Octylphenol (OIPs)</td><td>D</td><td>embryon</td><td></td><td></td><td>25</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Bisphenol A (OIPs)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>7</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan="20"><strong>Physiology</strong></td></tr><tr><td>Simazine (Agroch.)</td><td>D</td><td>embryon</td><td></td><td></td><td>8</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Simazine (Agroch.)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td></td><td>8</td><td>7</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Cypermethrin (Agroch.)</td><td>D</td><td>larva</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>6</td><td>6</td><td>6</td><td>6</td></tr><tr><td>Cypermethrin (Agroch.)</td><td>G</td><td>larva</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>6</td><td>6</td><td>6</td><td>6</td><td>6</td></tr><tr><td>Metformin (HCPs)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>16</td><td>13</td><td>12</td><td>9</td><td>17</td><td>7</td></tr><tr><td>Metformin (HCPs)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>12</td><td>14</td><td>8</td><td>12</td><td>12</td><td>12</td></tr><tr><td>Carbamazepine (HCPs)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>30</td><td>33</td><td>31</td><td>31</td><td>28</td><td>12</td></tr><tr><td>Carbamazepine (HCPs)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>46</td><td>58</td><td>48</td><td>98</td><td>64</td><td>46</td></tr><tr><td>Estrone (HCPs)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>9</td><td>5</td><td>5</td><td>109</td><td>5</td><td>5</td></tr><tr><td>Estrone (HCPs)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>135</td><td>135</td><td>135</td></tr><tr><td>Calcium (Metals)</td><td>D</td><td>larva</td><td>18</td><td>13</td><td>14</td><td>14</td><td>13</td><td>16</td><td>15</td><td>13</td><td>11</td><td>12</td><td>14</td><td>14</td><td>12</td><td>14</td><td>15</td><td>10</td></tr><tr><td>Calcium (Metals)</td><td>G</td><td>larva</td><td>23</td><td>29</td><td>27</td><td>27</td><td>23</td><td>23</td><td>22</td><td>27</td><td>27</td><td>26</td><td>25</td><td>24</td><td>25</td><td>23</td><td>23</td><td>28</td></tr><tr><td>Copper (Metals)</td><td>D</td><td>larva</td><td></td><td></td><td></td><td>19</td><td>5</td><td></td><td>12</td><td></td><td></td><td>7</td><td>7</td><td>6</td><td>5</td><td></td><td></td><td>5</td></tr><tr><td>Copper (Metals)</td><td>G</td><td>larva</td><td></td><td></td><td></td><td>11</td><td>29</td><td>8</td><td>14</td><td>9</td><td>10</td><td>19</td><td>6</td><td>6</td><td>7</td><td>7</td><td>10</td><td>7</td></tr><tr><td>Phenol, 4-nonyl-, branched (OIPs)</td><td>D</td><td>embryon</td><td></td><td>18</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Phenol, 4-nonyl-, branched (OIPs)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>6</td><td></td><td></td></tr><tr><td>Dioctyl phthalate (OIPs)</td><td>D</td><td>embryon</td><td></td><td>10</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Dioctyl phthalate (OIPs)</td><td>D</td><td>larva</td><td></td><td>14</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Benzolalpyrene (PAHs)</td><td>D</td><td>embryon</td><td></td><td>15</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Fluoranthene (PAHs)</td><td>D</td><td>embryon</td><td></td><td>8</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td colspan="20"><strong>Mortality</strong></td></tr><tr><td>Lead (Metals)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td>29</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Lead (Metals)</td><td>G</td><td>embryon</td><td></td><td></td><td></td><td>10</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>4-tert-Octylphenol (OIPs)</td><td>D</td><td>larva</td><td></td><td>48</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Bisphenol A (OIPs)</td><td>D</td><td>embryon</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>7</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Dioctyl phthalate (OIPs)</td><td>D</td><td>larva</td><td></td><td>6</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></tbody></table>

## 5. Discussion

### A. Summary of main results

Using only quantified environmental data, we have seen that there was a toxic risk for the fish taxon (msPAF<sub>F-AM</sub> > Th<sub>5%</sub>) in the Garonne spawning grounds for each year of the study period. In the Dordogne, this risk was only present for part of the period (2006, 2007, 2008, 2010, 2011, 2013 and 2015). Furthermore, at quantified environmental concentrations, msPAF<sub>F-T</sub> values were twice as high in the Garonne spawning grounds (~8% > Th<sub>5%</sub>) as in the Dordogne spawning grounds (~4% < Th<sub>5%</sub>). There was also a high degree of variability within spawning grounds each year (high standard
deviations), with significant differences in msPAF<sub>F-AM</sub> values between stations in the same spawning ground. For these indicators (msPAF<sub>F-AM</sub> and msPAF<sub>F-T</sub>), the use of quantified and unquantified environmental data overestimated the values obtained only in 2007 and 2019 in the Dordogne and from 2019 to 2021 in the Garonne.

In terms of life stage sensitivity, using quantified environmental data, only larval physiology and larval development in both spawning grounds, and adult physiology in Garonne spawning grounds had msPAF<sub>SE-T</sub> values indicating a potential toxic risk (> Th<sub>5%</sub>). Using quantified environmental data, the embryonic stage had msPAF<sub>SE-T</sub> values close to Th<sub>5%</sub> (for effect on physiology) and the juvenile stage was the least impacted (msPAF<sub>SE-T</sub> max. of 1.32%). Using both quantified and unquantified data, all life stages showed values above Th<sub>5%</sub>, for at least one effect. Regardless of the environmental data used, only embryos showed msPAF<sub>SE-T</sub> values associated with mortality effects exceeding 1%.

Using quantified and unquantified environmental data, different categories of chemical compounds strongly contributed to msPAF<sub>SE-AM</sub> specific to early life stages of fish at values above Th<sub>5%</sub>. In both spawning grounds, metals (■) exceeded Th<sub>5%</sub> for embryonic development, embryonic mortality, larval development and larval physiology. Although monitored from 2016, HCPs (■) exceeded Th<sub>5%</sub> in both spawning grounds for embryonic behavior, embryonic physiology, embryonic development and larval behavior. Although generally presenting low contributions, agrochemicals (■) exceeded Th<sub>5%</sub> for embryonic physiology and larval physiology in both spawning grounds. Only in a few years in the Dordogne did OIPs (■) contribute values above Th<sub>5%</sub> for embryonic development, embryonic physiology, embryonic behavior, embryonic mortality, larval development, larval physiology and larval mortality. For PAHs (■), a contribution exceeding Th<sub>5%</sub> was visible only in 2007 for embryonic development and embryonic physiology in the Dordogne. PCBs (■) and PFASs (●) did not show significant msPAF<sub>SE-AM</sub> values. For early life stages of fish, compounds individually exceeding Th<sub>5%</sub> at quantified environmental values were : calcium (metals), copper (metals), zinc (metals), lead (metals), simazine (agrochemicals), cypermethrin (agrochemicals), metformin (HCPs), carbamazepine (HCPs), bisphenol A (OIPs), phenol, 4-nonyl-, branched (OIPs) and 4-tert-octylphenol (OIPs).

## B. Toxic effects of individual substances contributing to PAF

For early life stages (embryos and larvae), the individual contribution of each substance was studied, and chemical compounds exceeding the Th<sub>5%</sub> were identified, in particular for quantified environmental data.

### a. Metals

The four metals (calcium, zinc, copper and lead) that exceeded the Th<sub>5%</sub> also did so at quantified environmental values. These compounds had quantified concentrations ranging from 18.1 to 50.4 mg/L for calcium, from 2.71E-05 to 7.94E-03 mg/L for copper, from 3.16E-05 to 7.94E-03 mg/L for lead and from 2.12E-04 to 3.21E-02 mg/L for zinc.
deviations), with significant differences in msPAF<sub>F-AM</sub> values between stations in the same spawning ground. For these indicators (msPAF<sub>F-AM</sub> and msPAF<sub>F-T</sub>), the use of quantified and unquantified environmental data overestimated the values obtained only in 2007 and 2019 in the Dordogne and from 2019 to 2021 in the Garonne.

In terms of life stage sensitivity, using quantified environmental data, only larval physiology and larval development in both spawning grounds, and adult physiology in Garonne spawning grounds had msPAF<sub>SE-T</sub> values indicating a potential toxic risk (> Th<sub>5%</sub>). Using quantified environmental data, the embryonic stage had msPAF<sub>SE-T</sub> values close to Th<sub>5%</sub> (for effect on physiology) and the juvenile stage was the least impacted (msPAF<sub>SE-T</sub> max. of 1.32%). Using both quantified and unquantified data, all life stages showed values above Th<sub>5%</sub>, for at least one effect. Regardless of the environmental data used, only embryos showed msPAF<sub>SE-T</sub> values associated with mortality effects exceeding 1%.

Using quantified and unquantified environmental data, different categories of chemical compounds strongly contributed to msPAF<sub>SE-AM</sub> specific to early life stages of fish at values above Th<sub>5%</sub>. In both spawning grounds, metals (■) exceeded Th<sub>5%</sub> for embryonic development, embryonic mortality, larval development and larval physiology. Although monitored from 2016, HCPs (■) exceeded Th<sub>5%</sub> in both spawning grounds for embryonic behavior, embryonic physiology, embryonic development and larval behavior. Although generally presenting low contributions, agrochemicals (■) exceeded Th<sub>5%</sub> for embryonic physiology and larval physiology in both spawning grounds. Only in a few years in the Dordogne did OIPs (■) contribute values above Th<sub>5%</sub> for embryonic development, embryonic physiology, embryonic behavior, embryonic mortality, larval development, larval physiology and larval mortality. For PAHs (■), a contribution exceeding Th<sub>5%</sub> was visible only in 2007 for embryonic development and embryonic physiology in the Dordogne. PCBs (■) and PFASs (●) did not show significant msPAF<sub>SE-AM</sub> values. For early life stages of fish, compounds individually exceeding Th<sub>5%</sub> at quantified environmental values were : calcium (metals), copper (metals), zinc (metals), lead (metals), simazine (agrochemicals), cypermethrin (agrochemicals), metformin (HCPs), carbamazepine (HCPs), bisphenol A (OIPs), phenol, 4-nonyl-, branched (OIPs) and 4-tert-octylphenol (OIPs).

## B. Toxic effects of individual substances contributing to PAF

For early life stages (embryos and larvae), the individual contribution of each substance was studied, and chemical compounds exceeding the Th<sub>5%</sub> were identified, in particular for quantified environmental data.

### a. Metals

The four metals (calcium, zinc, copper and lead) that exceeded the Th<sub>5%</sub> also did so at quantified environmental values. These compounds had quantified concentrations ranging from 18.1 to 50.4 mg/L for calcium, from 2.71E-05 to 7.94E-03 mg/L for copper, from 3.16E-05 to 7.94E-03 mg/L for lead and from 2.12E-04 to 3.21E-02 mg/L for zinc.
For calcium, the HC50<sub>SE</sub> associated with larval development and larval physiology was both 87.1 mg/L, obtained with two tests carried out on the same species. For copper, the HC50<sub>SE</sub> associated with embryonic development was 1.09E-02 mg/L, obtained with only one test, and the HC50<sub>SE</sub> associated with larval physiology was 5.32E-03 mg/L, obtained with two tests conducted on the same species. For zinc, the HC50<sub>SE</sub> associated with larval development was 2.55E-01 mg/L, obtained with three tests performed on the same species. For lead, the HC50<sub>SE</sub> associated with embryonic mortality was 1.36E-02 mg/L, obtained using a single test.

Historically, anthropogenic contamination by metals (cadmium, zinc, copper and lead) in the Garonne has been associated with the Riou-Mort river, a watercourse flowing into the Garonne downstream of the allis shad spawning grounds (Audry et al., 2004). Other sources have also been identified. In the Dordogne and Tarn rivers (flowing into the Garonne upstream of the allis shad spawning grounds), metallic contamination has been recorded, but this only concerned vanadium and chromium (Grousset et al., 1999).

However, in the GGD catchment, where agricultural activity is high (Faggiano et al., 2010), metals can be used as fungicides in vineyards: copper in Bordeaux mixture (in French, "bouillie-bordelaise") and zinc (Bernard, 2018; Lucas et al., 2021). As a result, these metals used in agriculture can leach into watercourses and even sediment (Bonten et al., 2008). However, sediment mobilization, intense flooding and local human activities can remobilize metals and thus increase the metal ratio in rivers (Audry et al., 2004).

The literature describes the effects of these metals. Hua et al. (2014) demonstrated that copper could inhibit hatching, increase malformations and deregulate behavior in Japanese medaka (Oryzias latipes) embryos. Additionally, Brungs (2011) revealed that zinc could induce premature hatching in fathead minnow (Pimephales promelas) embryos, potentially impacting larval fitness. As for lead, a study by Stominska (1998) showed that it could cause high embryo mortality in common carp (Cyprinus carpio).

Calcium has been particularly impactful during all the study period in both spawning grounds, but has been present at these concentrations in the GGD catchment historically (Ibarra et al., 2005), even before the decline of the allis shad population. Moreover, this calcium concentrations in limestone rivers (such as the Garonne and the Dordogne) may not be a cause for concern, as they can reduce the toxic effects of other compounds present in the water (Leynaud and Trocherie, 1980), and are even considered beneficial for freshwater fish (Arrignon, 1998). Furthermore, the toxicity values of the tests used for HC50<sub>SE</sub> calculation for calcium are derived from two studies mainly testing copper and secondarily calcium, in order to study the reduction in copper toxicity by the presence of calcium (Wu et al., 2007; Canli and Canli, 2015). These type of interactions between metals were not included in this study.
For calcium, the HC50<sub>SE</sub> associated with larval development and larval physiology was both 87.1 mg/L, obtained with two tests carried out on the same species. For copper, the HC50<sub>SE</sub> associated with embryonic development was 1.09E-02 mg/L, obtained with only one test, and the HC50<sub>SE</sub> associated with larval physiology was 5.32E-03 mg/L, obtained with two tests conducted on the same species. For zinc, the HC50<sub>SE</sub> associated with larval development was 2.55E-01 mg/L, obtained with three tests performed on the same species. For lead, the HC50<sub>SE</sub> associated with embryonic mortality was 1.36E-02 mg/L, obtained using a single test.

Historically, anthropogenic contamination by metals (cadmium, zinc, copper and lead) in the Garonne has been associated with the Riou-Mort river, a watercourse flowing into the Garonne downstream of the allis shad spawning grounds (Audry et al., 2004). Other sources have also been identified. In the Dordogne and Tarn rivers (flowing into the Garonne upstream of the allis shad spawning grounds), metallic contamination has been recorded, but this only concerned vanadium and chromium (Grousset et al., 1999).

However, in the GGD catchment, where agricultural activity is high (Faggiano et al., 2010), metals can be used as fungicides in vineyards: copper in Bordeaux mixture (in French, "bouillie-bordelaise") and zinc (Bernard, 2018; Lucas et al., 2021). As a result, these metals used in agriculture can leach into watercourses and even sediment (Bonten et al., 2008). However, sediment mobilization, intense flooding and local human activities can remobilize metals and thus increase the metal ratio in rivers (Audry et al., 2004).

The literature describes the effects of these metals. Hua et al. (2014) demonstrated that copper could inhibit hatching, increase malformations and deregulate behavior in Japanese medaka (Oryzias latipes) embryos. Additionally, Brungs (2011) revealed that zinc could induce premature hatching in fathead minnow (Pimephales promelas) embryos, potentially impacting larval fitness. As for lead, a study by Stominska (1998) showed that it could cause high embryo mortality in common carp (Cyprinus carpio).

Calcium has been particularly impactful during all the study period in both spawning grounds, but has been present at these concentrations in the GGD catchment historically (Ibarra et al., 2005), even before the decline of the allis shad population. Moreover, this calcium concentrations in limestone rivers (such as the Garonne and the Dordogne) may not be a cause for concern, as they can reduce the toxic effects of other compounds present in the water (Leynaud and Trocherie, 1980), and are even considered beneficial for freshwater fish (Arrignon, 1998). Furthermore, the toxicity values of the tests used for HC50<sub>SE</sub> calculation for calcium are derived from two studies mainly testing copper and secondarily calcium, in order to study the reduction in copper toxicity by the presence of calcium (Wu et al., 2007; Canli and Canli, 2015). These type of interactions between metals were not included in this study.
## b. Agrochemicals

Simazine (for embryonic physiology in the Garonne) and cypermethrin (for larval physiology in the Dordogne) were the only two agrochemicals to exceed the $Th_{5\%}$. These compounds had quantified concentrations ranging from 8.13E-06 to 7.40E-05 mg/L for simazine in the Garonne and were 2.50E-05 mg/L for cypermethrin in the Dordogne. These chemicals had an $HC_{50}_{SE}$ of 2.05E-04 mg/L for simazine and 8.25E-05 mg/L for cypermethrin. These data used one toxicity data and five toxicity data from two species, respectively.

Simazine is an herbicide used to control weeds in olive groves and vineyards (Oropesa et al., 2009). Devault et al. (2007) revealed that this herbicide was particularly present in the Garonne and its tributaries, and that this contamination could be linked to the chemical treatment of orchards ending up in the Tarn. This agrochemical was impacting in 2010 and 2011 in our study despite having been banned in 2003 in France (Guibal et al., 2018). The study by Velisek et al. (2012) demonstrated that simazine affected the growth and histology (especially the kidney) of early life stages of common carp (*Cyprinus carpio*) at environmentally relevant concentrations.

Cypermethrin is an insecticide used to control ticks and mites, which can therefore be used both in agriculture and in households (Farag et al., 2021). This substance is not banned, despite the damage it can cause. Indeed, the study by Carriquiriborde et al. (2009) revealed that this substance can affect larval growth in pejerrey (*Odontesthes bonariensis*).

## c. Hygiene and Care Products (HCPs)

Estrone has been shown to be problematic for the development, physiology and behavior of embryos and the behavior of larvae. However, no values at quantified environmental concentrations exceeded the $Th_{5\%}$. Estrone is considered an endocrine disruptor and a threat to living organisms, even at low concentrations (1.00E-07 to 1.00E-06 mg/L) (Sami and Fatma, 2019). In this study, average annual quantified concentrations range from 5.75E-06 to 7.80E-06 mg/L in the Garonne, well above the low effect-inducing concentrations.

This hormone is synthesized naturally, notably during the menstrual period (Johnson and Williams, 2004) and can also come from the transformation of estradiol (present in pills) into estrone under certain conditions (Eaton, 2022). In the study by Destrieux (2018), estrone was one of the most problematic molecules downstream of the city of Toulouse's discharges, despite a removal efficiency by wastewater treatment plants of over 75%. The remaining 25% could correspond to what is not eliminated and therefore to the values quantified in the Garonne (generating in this study a PAFi max. of 4.2%). The high values quantified in our study may be related to its partial elimination during wastewater treatment processes (Racz and Goel, 2010; Manickum and John, 2014) or with strong transformation from estradiol under the conditions present in these wastewater treatment processes (Eaton, 2022).
## b. Agrochemicals

Simazine (for embryonic physiology in the Garonne) and cypermethrin (for larval physiology in the Dordogne) were the only two agrochemicals to exceed the $Th_{5\%}$. These compounds had quantified concentrations ranging from 8.13E-06 to 7.40E-05 mg/L for simazine in the Garonne and were 2.50E-05 mg/L for cypermethrin in the Dordogne. These chemicals had an $HC_{50}_{SE}$ of 2.05E-04 mg/L for simazine and 8.25E-05 mg/L for cypermethrin. These data used one toxicity data and five toxicity data from two species, respectively.

Simazine is an herbicide used to control weeds in olive groves and vineyards (Oropesa et al., 2009). Devault et al. (2007) revealed that this herbicide was particularly present in the Garonne and its tributaries, and that this contamination could be linked to the chemical treatment of orchards ending up in the Tarn. This agrochemical was impacting in 2010 and 2011 in our study despite having been banned in 2003 in France (Guibal et al., 2018). The study by Velisek et al. (2012) demonstrated that simazine affected the growth and histology (especially the kidney) of early life stages of common carp (*Cyprinus carpio*) at environmentally relevant concentrations.

Cypermethrin is an insecticide used to control ticks and mites, which can therefore be used both in agriculture and in households (Farag et al., 2021). This substance is not banned, despite the damage it can cause. Indeed, the study by Carriquiriborde et al. (2009) revealed that this substance can affect larval growth in pejerrey (*Odontesthes bonariensis*).

## c. Hygiene and Care Products (HCPs)

Estrone has been shown to be problematic for the development, physiology and behavior of embryos and the behavior of larvae. However, no values at quantified environmental concentrations exceeded the $Th_{5\%}$. Estrone is considered an endocrine disruptor and a threat to living organisms, even at low concentrations (1.00E-07 to 1.00E-06 mg/L) (Sami and Fatma, 2019). In this study, average annual quantified concentrations range from 5.75E-06 to 7.80E-06 mg/L in the Garonne, well above the low effect-inducing concentrations.

This hormone is synthesized naturally, notably during the menstrual period (Johnson and Williams, 2004) and can also come from the transformation of estradiol (present in pills) into estrone under certain conditions (Eaton, 2022). In the study by Destrieux (2018), estrone was one of the most problematic molecules downstream of the city of Toulouse's discharges, despite a removal efficiency by wastewater treatment plants of over 75%. The remaining 25% could correspond to what is not eliminated and therefore to the values quantified in the Garonne (generating in this study a PAFi max. of 4.2%). The high values quantified in our study may be related to its partial elimination during wastewater treatment processes (Racz and Goel, 2010; Manickum and John, 2014) or with strong transformation from estradiol under the conditions present in these wastewater treatment processes (Eaton, 2022).
Both metformin and carbamazepine affected embryo physiology at environmental values in the Garonne and Dordogne spawning grounds. These compounds had quantified concentrations ranging from 1.51E-04 to 3.68E-04 mg/L for metformin and from 6.17E-06 to 2.20E-05 mg/L for carbamazepine. The calculated HC50<sub>SE</sub> were 1.09E-03 mg/L (from 1 test) and 1.09E-05 mg/L (from 3 tests on the same species), respectively.

Metformin is the most widely used oral hypoglycemic agent for the treatment of diabetes (Juneja et al., 2022). In the study by Crago and Klaper (2018), at relevant environmental concentrations, metformin was found to have oestrogenic activities (i.e. mimicking or antagonizing the actions of natural estrogens), thus acting as an endocrine disruptor. Moreover, it may induce altered social and mating behavior in fish (Kallivretaki et al., 2007).

Carbamazepine is used to treat epilepsy, schizophrenia, bipolar disorder, among others (Pellock, 1987). In the study by Van Den Brandhof and Montforts (2010), embryos developed growth retardation and cardiac abnormalities. After elimination, these drugs must pass through wastewater treatment plants (Lévi, 2020). However, the study by Aminot (2013) showed an elimination efficiency of less than 10% for carbamazepine and close to 75% for metformin for the treatment plants present in the Garonne. This could explain the high concentrations found in our study.

### d. Other industrial products (including PAHs, PFASs and PCBs)

Seven of the substances classified as industrial pollutants (OIPs, PAHs, PCBs, PFASs) stand out. These are tributylstannane (OIPs), dioctyl phthalate (OIPs), phenol, 4-nonyl-, branched (OIPs), 4-tert-octylphenol (OIPs), bisphenol A (OIPs), benzo[a]pyrene (PAHs) and fluoranthene (PAHs). At quantified environmental concentrations, bisphenol A (embryonic development, embryonic behavior, embryonic mortality and larval development in the Dordogne), 4-tert-octylphenol (larval mortality in the Dordogne) and phenol, 4-nonyl-, branched (embryonic physiology in the Garonne) exceeded the Th<sub>5%</sub>. These compounds had quantified concentrations ranging from 7.50E-05 to 1.19E-01 mg/L for bisphenol A, from 1.38E-05 to 2.88E-04 mg/L for 4-tert-octylphenol and from 4.02E-07 to 1.02E-03 mg/L for phenol, 4-nonyl-, branched. The resulting HC50<sub>SE</sub> were, respectively, 0.36, 0.896, 0.868 and 7.44E-03 mg/L for bisphenol A, 3.48E-03 mg/L for 4-tert-octylphenol and 9.10E-03 mg/L for phenol, 4-nonyl-, branched.

Tributylstannane (or tributyltin) is an endocrine disruptor commonly used as a biocide in antifouling boat paints but also for mucus control in paper mills and disinfection of industrial cooling water (Bushong et al., 1988; Antizar-Ladislao, 2008). The study by Ortiz-Villanueva et al. (2018) demonstrated that this substance caused metabolic alterations in zebrafish (*Danio rerio*) embryos. Dioctyl phthalate is the phthalate most commonly used as a plasticizer to make materials flexible (Rowdhwal and Chen, 2018). In the study by Chen et al. (2014), this endocrine disruptor induced various effects (death, tail curvature, necrosis, cardiac edema and lack of response to touch) in zebrafish (*Danio rerio*) embryos but also enhanced estrogenic activity in Japanese medaka (*Oryzias latipes*) embryos.
Both metformin and carbamazepine affected embryo physiology at environmental values in the Garonne and Dordogne spawning grounds. These compounds had quantified concentrations ranging from 1.51E-04 to 3.68E-04 mg/L for metformin and from 6.17E-06 to 2.20E-05 mg/L for carbamazepine. The calculated HC50SE were 1.09E-03 mg/L (from 1 test) and 1.09E-05 mg/L (from 3 tests on the same species), respectively.

Metformin is the most widely used oral hypoglycemic agent for the treatment of diabetes (Juneja et al., 2022). In the study by Crago and Klaper (2018), at relevant environmental concentrations, metformin was found to have oestrogenic activities (i.e. mimicking or antagonizing the actions of natural estrogens), thus acting as an endocrine disruptor. Moreover, it may induce altered social and mating behavior in fish (Kallivretaki et al., 2007).

Carbamazepine is used to treat epilepsy, schizophrenia, bipolar disorder, among others (Pellock, 1987). In the study by Van Den Brandhof and Montforts (2010), embryos developed growth retardation and cardiac abnormalities. After elimination, these drugs must pass through wastewater treatment plants (Lévi, 2020). However, the study by Aminot (2013) showed an elimination efficiency of less than 10% for carbamazepine and close to 75% for metformin for the treatment plants present in the Garonne. This could explain the high concentrations found in our study.

### d. Other industrial products (including PAHs, PFASs and PCBs)

Seven of the substances classified as industrial pollutants (OIPs, PAHs, PCBs, PFASs) stand out. These are tributylstannane (OIPs), dioctyl phthalate (OIPs), phenol, 4-nonyl-, branched (OIPs), 4-tert-octylphenol (OIPs), bisphenol A (OIPs), benzo[a]pyrene (PAHs) and fluoranthene (PAHs). At quantified environmental concentrations, bisphenol A (embryonic development, embryonic behavior, embryonic mortality and larval development in the Dordogne), 4-tert-octylphenol (larval mortality in the Dordogne) and phenol, 4-nonyl-, branched (embryonic physiology in the Garonne) exceeded the Th5%. These compounds had quantified concentrations ranging from 7.50E-05 to 1.19E-01 mg/L for bisphenol A, from 1.38E-05 to 2.88E-04 mg/L for 4-tert-octylphenol and from 4.02E-07 to 1.02E-03 mg/L for phenol, 4-nonyl-, branched. The resulting HC50SE were, respectively, 0.36, 0.896, 0.868 and 7.44E-03 mg/L for bisphenol A, 3.48E-03 mg/L for 4-tert-octylphenol and 9.10E-03 mg/L for phenol, 4-nonyl-, branched.

Tributylstannane (or tributyltin) is an endocrine disruptor commonly used as a biocide in antifouling boat paints but also for mucus control in paper mills and disinfection of industrial cooling water (Bushong et al., 1988; Antizar-Ladislao, 2008). The study by Ortiz-Villanueva et al. (2018) demonstrated that this substance caused metabolic alterations in zebrafish (Danio rerio) embryos. Dioctyl phthalate is the phthalate most commonly used as a plasticizer to make materials flexible (Rowdhwal and Chen, 2018). In the study by Chen et al. (2014), this endocrine disruptor induced various effects (death, tail curvature, necrosis, cardiac edema and lack of response to touch) in zebrafish (Danio rerio) embryos but also enhanced estrogenic activity in Japanese medaka (Oryzias latipes) embryos.
Phenol, 4-nonyl-, branched is an estrogenic compound (Jin et al., 2010). The study by Xu et al. (2013) revealed that this endocrine perturbator induced an increase in reactive oxygen species in zebrafish (*Danio rerio*) embryos. 4-tert-octylphenol is an endocrine disruptor used in detergents, paints, tanneries, etc. (Du et al., 2022). The study by Madsen et al. (2006) demonstrated that 4-tert octylphenol induced vitellogenin production and decreased gonad weight in European flounder (*Platichthys flesus*). Bisphenol A is an endocrine disruptor with estrogenic activities that was mainly used in the production of polycarbonate plastics (70%) and epoxy resins (20%) (Eladak et al., 2015). The study by Gao et al. (2022) demonstrated that this substance has effects on both embryos (spontaneous hatching, effects on behavior and heart rate) and larvae (yolk sac and pericardial edema and spinal deformation) of zebrafish (*Danio rerio*).

Benzolpyrene and fluoranthene contamination is mainly the result of incomplete combustion in waste incineration processes, rubber tires manufacturing and agrochemicals production (Patel et al., 2020). PAHs are known to be endocrine disruptors and to have an impact on embryonic development (cleavage phase, heart development and other malformations), thus potentially impacting larval fitness (Honda and Suzuki, 2020).

With regard to PFASs and PCBs, no substance contributed particularly to msPAF. For PCBs, no values were available for embryos. The highest values (PAFi) were 0.005% of potentially affected species for PFASs and 0.320% of potentially affected species for PCBs.

### C. Main results of other studies using the PAF method

#### a. GGD catchment

This work is the first, at the GGD catchment scale, to use the (ms)PAF method by specifically estimating toxic pressure for each life stage of a particular taxon (fish) with such a wide range of substances (n = 249) and over such a long period (16 years). However, other studies have used this method within the GGD catchment, but have only focused on agrochemicals (Faggiano et al., 2010; Shinn, 2010). This can be explained by the strong presence of agricultural activities in the GGD catchment, and therefore the problem of agrochemicals use (Devault et al., 2007, see Corin Land Cover on Figure 4).

The study by Faggiano et al. (2010), located in the Adour-Garonne catchment, used the maximum quantified environmental concentration of agrochemicals to estimate their worst-case risk. In addition, they differentiated agrochemicals according to their toxic modes of action, making it possible to refine the analysis by not considering the same mode of action for each substance. For instance, species sensitivity was compared for different groups of substances: inhibitors of acetylcholinesterase activity, seedling growth inhibitors, inhibitors of photosynthetic activity, plant growth regulators, among others. From May to December 2006, the maximum PAF value (3.7%) was attributed to carbofuran, with a maximum quantified value of 4.50E-03 mg/L. In our study, annual quantified carbofuran averages ranged from 1.75E-05 to 5.55E-05 mg/L between 2006 and 2008 in Garonne spawning grounds.
Phenol, 4-nonyl-, branched is an estrogenic compound (Jin et al., 2010). The study by Xu et al. (2013) revealed that this endocrine perturbator induced an increase in reactive oxygen species in zebrafish (*Danio rerio*) embryos. 4-tert-octylphenol is an endocrine disruptor used in detergents, paints, tanneries, etc. (Du et al., 2022). The study by Madsen et al. (2006) demonstrated that 4-tert octylphenol induced vitellogenin production and decreased gonad weight in European flounder (*Platichthys flesus*). Bisphenol A is an endocrine disruptor with estrogenic activities that was mainly used in the production of polycarbonate plastics (70%) and epoxy resins (20%) (Eladak et al., 2015). The study by Gao et al. (2022) demonstrated that this substance has effects on both embryos (spontaneous hatching, effects on behavior and heart rate) and larvae (yolk sac and pericardial edema and spinal deformation) of zebrafish (*Danio rerio*).

Benzolpyrene and fluoranthene contamination is mainly the result of incomplete combustion in waste incineration processes, rubber tires manufacturing and agrochemicals production (Patel et al., 2020). PAHs are known to be endocrine disruptors and to have an impact on embryonic development (cleavage phase, heart development and other malformations), thus potentially impacting larval fitness (Honda and Suzuki, 2020).

With regard to PFASs and PCBs, no substance contributed particularly to msPAF. For PCBs, no values were available for embryos. The highest values (PAFi) were 0.005% of potentially affected species for PFASs and 0.320% of potentially affected species for PCBs.

### C. Main results of other studies using the PAF method

#### a. GGD catchment

This work is the first, at the GGD catchment scale, to use the (ms)PAF method by specifically estimating toxic pressure for each life stage of a particular taxon (fish) with such a wide range of substances (n = 249) and over such a long period (16 years). However, other studies have used this method within the GGD catchment, but have only focused on agrochemicals (Faggiano et al., 2010; Shinn, 2010). This can be explained by the strong presence of agricultural activities in the GGD catchment, and therefore the problem of agrochemicals use (Devault et al., 2007, see Corin Land Cover on Figure 4).

The study by Faggiano et al. (2010), located in the Adour-Garonne catchment, used the maximum quantified environmental concentration of agrochemicals to estimate their worst-case risk. In addition, they differentiated agrochemicals according to their toxic modes of action, making it possible to refine the analysis by not considering the same mode of action for each substance. For instance, species sensitivity was compared for different groups of substances: inhibitors of acetylcholinesterase activity, seedling growth inhibitors, inhibitors of photosynthetic activity, plant growth regulators, among others. From May to December 2006, the maximum PAF value (3.7%) was attributed to carbofuran, with a maximum quantified value of 4.50E-03 mg/L. In our study, annual quantified carbofuran averages ranged from 1.75E-05 to 5.55E-05 mg/L between 2006 and 2008 in Garonne spawning grounds.
The study by Faggiano et al. (2010) was then extended to use the SOM (Self Organizing Map) method to classify sites according to the risk they represent on the basis of their contaminant composition (Wang et al., 2020). The results showed a low agrochemical contamination risk for aquatic organisms at 83% of the sites studied. However, in Lot-et-Garonne, with an average msPAF value of over 1%, the risk was high for primary producers, invertebrates and fish. In a later report on the same study by Faggiano (2013), the years 2007 and 2008 showed maximum values of less than 1 and 1.5% of potentially affected species, respectively. Thus, this study agrees with ours in that no significant agrochemical-associated msPAF values specific to fish taxon were observed. The maximum agrochemical-associated msPAF value specific to fish taxon being 1.64% in 2013 in the Garonne near its confluence with the Lot.

Similarly, in the Adour-Garonne catchment, the study by Shinn (2010) used the msPAF method, also differentiating agrochemicals according to their toxic modes of action. Here, the PAF method was used to confirm or reject the characterization of the study sites (poor, moderate and good quality) according to the toxic pressure generated by agrochemical contamination from 2006 to 2008. Sites classified as poor quality had msPAF values of almost 10%, while medium and high quality sites had msPAF values of less than 0.1%. Thus, based on the results of the previous study and the results of this work, using only quantified values, the allis shad spawning grounds of the Dordogne and Garonne rivers would not be characterized as moderate or good quality, but rather poor quality.

### b. Europe

A number of European studies have been carried out using this method (e.g., Carafa et al., 2011; Tuikka et al., 2011; Jesenska et al., 2013; Silva, 2015; Sarkis, 2018).

Carafa et al. (2011) studied 232 sites in Catalonia (Spain) between 2007 and 2008, using the PAF method and using the bioavailable fraction of 60 contaminants. They revealed that the risk of pollutant mixing exceeded 50% of potentially affected species at 10% of sites. In our study, the periodic average of msPAF exceeded 10% of potentially affected species for 60% of sites in the Dordogne and for 64% of sites in the Garonne, with 24% of sites exceeding 50%. In their study, 99% of water bodies were considered at risk (msPAF > 5%), compared with 62% in our case, based on quantified environmental data only. In addition, a higher ecological risk was observed near urban areas, mainly due to urban and industrial compounds (in particular metals and nonylphenol) and agrochemicals (in particular chlorpyrifos). Metals were a major contributor to msPAF in our study. Chlorpyrifos was monitored but not quantified in spawning grounds in the GGD catchment, and nonylphenol was quantified in the Garonne (2.50E-04 to 1.33E-03 mg/L) and in the Dordogne (4.02E-07 to 2.16E-04 mg/L) spawning grounds. This higher toxic risk near urban areas, combined with the lack of efficiency of water treatment plants, means that contamination of the Garonne is largely due to discharges of treated water (Aminot, 2013).
The study by Faggiano et al. (2010) was then extended to use the SOM (Self Organizing Map) method to classify sites according to the risk they represent on the basis of their contaminant composition (Wang et al., 2020). The results showed a low agrochemical contamination risk for aquatic organisms at 83% of the sites studied. However, in Lot-et-Garonne, with an average msPAF value of over 1%, the risk was high for primary producers, invertebrates and fish. In a later report on the same study by Faggiano (2013), the years 2007 and 2008 showed maximum values of less than 1 and 1.5% of potentially affected species, respectively. Thus, this study agrees with ours in that no significant agrochemical-associated msPAF values specific to fish taxon were observed. The maximum agrochemical-associated msPAF value specific to fish taxon being 1.64% in 2013 in the Garonne near its confluence with the Lot.

Similarly, in the Adour-Garonne catchment, the study by Shinn (2010) used the msPAF method, also differentiating agrochemicals according to their toxic modes of action. Here, the PAF method was used to confirm or reject the characterization of the study sites (poor, moderate and good quality) according to the toxic pressure generated by agrochemical contamination from 2006 to 2008. Sites classified as poor quality had msPAF values of almost 10%, while medium and high quality sites had msPAF values of less than 0.1%. Thus, based on the results of the previous study and the results of this work, using only quantified values, the allis shad spawning grounds of the Dordogne and Garonne rivers would not be characterized as moderate or good quality, but rather poor quality.

### b. Europe

A number of European studies have been carried out using this method (e.g., Carafa et al., 2011; Tuikka et al., 2011; Jesenska et al., 2013; Silva, 2015; Sarkis, 2018).

Carafa et al. (2011) studied 232 sites in Catalonia (Spain) between 2007 and 2008, using the PAF method and using the bioavailable fraction of 60 contaminants. They revealed that the risk of pollutant mixing exceeded 50% of potentially affected species at 10% of sites. In our study, the periodic average of msPAF exceeded 10% of potentially affected species for 60% of sites in the Dordogne and for 64% of sites in the Garonne, with 24% of sites exceeding 50%. In their study, 99% of water bodies were considered at risk (msPAF > 5%), compared with 62% in our case, based on quantified environmental data only. In addition, a higher ecological risk was observed near urban areas, mainly due to urban and industrial compounds (in particular metals and nonylphenol) and agrochemicals (in particular chlorpyrifos). Metals were a major contributor to msPAF in our study. Chlorpyrifos was monitored but not quantified in spawning grounds in the GGD catchment, and nonylphenol was quantified in the Garonne (2.50E-04 to 1.33E-03 mg/L) and in the Dordogne (4.02E-07 to 2.16E-04 mg/L) spawning grounds. This higher toxic risk near urban areas, combined with the lack of efficiency of water treatment plants, means that contamination of the Garonne is largely due to discharges of treated water (Aminot, 2013).
In another study, Jesenska et al. (2013) studied the toxic risk of seven herbicides from 1998 to 2009 in the Scheldt catchment (Belgium). Despite an estimated decreasing risk throughout the period, the risk associated with herbicides was close to 40% of potentially affected species in the primary producer community. Moreover, they observed a drop in simazine concentrations from 1998 to 2009. In our study, simazine had a concentration of 2.95E-05 mg/L in 2006 and 6.75E-05 mg/L in 2011 in the Garonne spawning grounds. After 2011, no more data were quantified for this chemical compound, but the average concentration of simazine increased to that date even though it has been banned in France since 2003.

Aditionnally, Silva (2015) studied the impact of agrochemical mixtures in the Mondego, Sado and Tejo catchments (Portugal) from 2002 to 2008. The msPAF values exceeded the Th5% in all catchments. Endosulfan had a particularly strong impact on fish species. In our study, endosulfan was monitored but not quantified in allis shad spawning grounds in the GGD catchment.

Finally, the study by Sarkis (2018) compared the contribution of stable contaminants and radionuclides to toxic impact up and down the Rhône (France) from 2010 to 2014. The msPAF values exceeded 30% of potentially affected species and showed a strong contribution of metals (copper, zinc, silver and nickel) and a stronger ecological impact downstream (potential contributions from Lyon, Valence and Avignon). This is consistent with the high copper and zinc contribution found in our study.

Thus, studies using the msPAF methodology in Europe show that water bodies with chemical pollution pose a significant toxic risk, particularly those close to highly urbanized areas. The msPAF method is often used to assess and monitor agrochemical pollution (see on a global scale De Zwart, 2005; Henning-de Jong et al., 2008; Echeverría-Sáenz et al., 2021; Nagai et al., 2022 for example). Our results and those of the previously cited studies are in line with those of Rorije et al. (2022). Indeed, they reveal that over 39% of Europe's water bodies are insufficiently protected against individual and combined chemical risks, although south-west France is not included in their study.

### D. Method limitations

Although useful, this method presented various biases, underestimating or overestimating the results. As indicated by Faggiano (2013), three classes of uncertainty surround this method: chemical exposure, toxic risk and ecological risk.

As far as chemical exposure is concerned, one of the main biases is the number of substances monitored. According to Posthuma et al. (2020), only ~0.2% of chemical compounds commercialized and potentially emitted into the environment are taken into account in water quality assessment and management in Europe. In addition, the renewal of these compounds is significant, since it is estimated that one organic molecule is created every 30 seconds (Pernet-Coudrier, 2008). According to the AEE (2019) report, ~100 000 chemical compounds are commercialized, so the toxic pressure studied in this report would represent only ~0.25% of what could potentially be present. However, it should be borne in mind that not all of these compounds are likely to be present in the
In another study, Jesenska et al. (2013) studied the toxic risk of seven herbicides from 1998 to 2009 in the Scheldt catchment (Belgium). Despite an estimated decreasing risk throughout the period, the risk associated with herbicides was close to 40% of potentially affected species in the primary producer community. Moreover, they observed a drop in simazine concentrations from 1998 to 2009. In our study, simazine had a concentration of 2.95E-05 mg/L in 2006 and 6.75E-05 mg/L in 2011 in the Garonne spawning grounds. After 2011, no more data were quantified for this chemical compound, but the average concentration of simazine increased to that date even though it has been banned in France since 2003.

Aditionnally, Silva (2015) studied the impact of agrochemical mixtures in the Mondego, Sado and Tejo catchments (Portugal) from 2002 to 2008. The msPAF values exceeded the Th5% in all catchments. Endosulfan had a particularly strong impact on fish species. In our study, endosulfan was monitored but not quantified in allis shad spawning grounds in the GGD catchment.

Finally, the study by Sarkis (2018) compared the contribution of stable contaminants and radionuclides to toxic impact up and down the Rhône (France) from 2010 to 2014. The msPAF values exceeded 30% of potentially affected species and showed a strong contribution of metals (copper, zinc, silver and nickel) and a stronger ecological impact downstream (potential contributions from Lyon, Valence and Avignon). This is consistent with the high copper and zinc contribution found in our study.

Thus, studies using the msPAF methodology in Europe show that water bodies with chemical pollution pose a significant toxic risk, particularly those close to highly urbanized areas. The msPAF method is often used to assess and monitor agrochemical pollution (see on a global scale De Zwart, 2005; Henning-de Jong et al., 2008; Echeverría-Sáenz et al., 2021; Nagai et al., 2022 for example). Our results and those of the previously cited studies are in line with those of Rorije et al. (2022). Indeed, they reveal that over 39% of Europe's water bodies are insufficiently protected against individual and combined chemical risks, although south-west France is not included in their study.

### D. Method limitations

Although useful, this method presented various biases, underestimating or overestimating the results. As indicated by Faggiano (2013), three classes of uncertainty surround this method: chemical exposure, toxic risk and ecological risk.

As far as chemical exposure is concerned, one of the main biases is the number of substances monitored. According to Posthuma et al. (2020), only ~0.2% of chemical compounds commercialized and potentially emitted into the environment are taken into account in water quality assessment and management in Europe. In addition, the renewal of these compounds is significant, since it is estimated that one organic molecule is created every 30 seconds (Pernet-Coudrier, 2008). According to the AEE (2019) report, ~100 000 chemical compounds are commercialized, so the toxic pressure studied in this report would represent only ~0.25% of what could potentially be present. However, it should be borne in mind that not all of these compounds are likely to be present in the
same place at the same time. Furthermore, the small number of quantified values in the environment for the monitored substances means that we cannot always take into account substances that may have an impact at low concentrations. According to the study by Rorije et al. (2022), only ~10% of the chemicals monitored (~10,000) are detected above their limit of detection or quantification due to a lack of sensitivity in the measurement instruments. Thus, the sample of quantified chemical compounds used in this report is certainly only a small fraction of what is actually present in the environment. In addition, depending on the priority of the chemical compounds, they are not monitored in the same way, which may limit the number of data available for a given period. The use of annual or periodic averages rather than maximum values may have minimized the maximum potential risk to the community studied. In this study, all the months of the year were included in the calculation of the average even though all is shown are only present on the spawning grounds for part of the year (April to October), which may have underestimated or overestimated the risk associated with the presence of chemical contaminants. In the case of underestimation, for instance, since agrochemicals are used during a specific period, they may be more concentrated in the water during certain months of the year (Cruz, 2015; Bernard, 2018). Furthermore, the extrapolations made (half of the LQ, aqueous phase of water and sediment-water partition coefficient) can degrade data quality. In addition, as mentioned above in relation to aluminum, human errors during data entry (erroneous value, change of unit, technological problem, etc.) can also degrade data quality to the point of rendering it unusable.

Regarding toxic risk, as indicated in the method, the quantity and quality of toxicity data have a major impact on the results. Here, the quantity of data was high overall (11 153) with an average ~70 tests from ~6 species per chemical compound. However, 72 chemicals had less than three different species for the HC50F calculation, 28 between four and five, 13 between six and ten and 20 with more than ten. In addition, 20 chemicals had less than three toxicity data for the HC50F calculation, 6 between four and five, 14 between six and ten and 93 with more than ten. As a result, many chemicals present a high number of species and tests for the HC50 calculation, if we refer to European Commission (2003) recommendation (minimum of 10 toxicity data from 8 defined taxa for ecosystem-representative HC50s). Moreover, as we have seen, most of the individually problematic chemical compounds used few tests and species to calculate HC50SE. However, the species most frequently used were mainly those used in laboratories and not found naturally in the GGD catchment (Williams et al., 2009). Furthermore, given that the method relies on an additive model, the more substances with toxicity data, the higher the msPAF values will be. Thus, some stations with fewer data than others may have underestimated the risk by calculating the average of all the stations on a spawning ground. However, toxicity data are not available for all substances. In our case, 133 of the 245 (~54%) substances included in the study had EC50 values. Hence, due to the lack of toxicity data, we lost information on ~46% of the substances quantified in the environment. Additionally, each chemical compound does not present toxicity values for all effects and for each life stage of each species, which limits comparison and restricts analysis of the results. Furthermore, in our study, the quality of toxicity data may have been impaired by the extrapolation of a significant
same place at the same time. Furthermore, the small number of quantified values in the environment for the monitored substances means that we cannot always take into account substances that may have an impact at low concentrations. According to the study by Rorije et al. (2022), only ~10% of the chemicals monitored (~10,000) are detected above their limit of detection or quantification due to a lack of sensitivity in the measurement instruments. Thus, the sample of quantified chemical compounds used in this report is certainly only a small fraction of what is actually present in the environment. In addition, depending on the priority of the chemical compounds, they are not monitored in the same way, which may limit the number of data available for a given period. The use of annual or periodic averages rather than maximum values may have minimized the maximum potential risk to the community studied. In this study, all the months of the year were included in the calculation of the average even though all is shown are only present on the spawning grounds for part of the year (April to October), which may have underestimated or overestimated the risk associated with the presence of chemical contaminants. In the case of underestimation, for instance, since agrochemicals are used during a specific period, they may be more concentrated in the water during certain months of the year (Cruz, 2015; Bernard, 2018). Furthermore, the extrapolations made (half of the LQ, aqueous phase of water and sediment-water partition coefficient) can degrade data quality. In addition, as mentioned above in relation to aluminum, human errors during data entry (erroneous value, change of unit, technological problem, etc.) can also degrade data quality to the point of rendering it unusable.

Regarding toxic risk, as indicated in the method, the quantity and quality of toxicity data have a major impact on the results. Here, the quantity of data was high overall (11 153) with an average ~70 tests from ~6 species per chemical compound. However, 72 chemicals had less than three different species for the HC50F calculation, 28 between four and five, 13 between six and ten and 20 with more than ten. In addition, 20 chemicals had less than three toxicity data for the HC50F calculation, 6 between four and five, 14 between six and ten and 93 with more than ten. As a result, many chemicals present a high number of species and tests for the HC50 calculation, if we refer to European Commission (2003) recommendation (minimum of 10 toxicity data from 8 defined taxa for ecosystem-representative HC50s). Moreover, as we have seen, most of the individually problematic chemical compounds used few tests and species to calculate HC50SE. However, the species most frequently used were mainly those used in laboratories and not found naturally in the GGD catchment (Williams et al., 2009). Furthermore, given that the method relies on an additive model, the more substances with toxicity data, the higher the msPAF values will be. Thus, some stations with fewer data than others may have underestimated the risk by calculating the average of all the stations on a spawning ground. However, toxicity data are not available for all substances. In our case, 133 of the 245 (~54%) substances included in the study had EC50 values. Hence, due to the lack of toxicity data, we lost information on ~46% of the substances quantified in the environment. Additionally, each chemical compound does not present toxicity values for all effects and for each life stage of each species, which limits comparison and restricts analysis of the results. Furthermore, in our study, the quality of toxicity data may have been impaired by the extrapolation of a significant
proportion of data from acute to chronic toxicity and/or from NOEC to EC50. Moreover, as mentioned by Jesenska et al. (2013) the use of the toxicity data may also alter the results (use of the most sensitive EC50 or the geometric mean of the EC50s). In addition, physico-chemical parameters such as temperature can modify the toxicity of a chemical compound (Philibert et al., 2023), phenomena that are not included in this method. As observed with calcium and copper, interactions between substances must also be considered. In reality, interactions between substances are more complex, with different modes of toxic action that can generate synergistic effects (increasing additive effects) or antagonistic effects (reducing additive effects). However, at low levels of chemical exposure, these interactions are rare or sufficiently insignificant (Faust et al., 2000). This bias is therefore not considered to be the most important, but must be taken into account.

For ecological risk, using the Th₅% as a reference to protect 95% of species in the fish taxon may distort the analysis of results, as it may not be sufficient to protect the community (Faggiano et al., 2010). Moreover, Pereira et al. (2018) revealed that freshwater communities are influenced in the field by environmental factors and biotic interactions, in addition to the presence of chemical mixtures; this was not taken into account in the method used. Finally, it was not possible to compare the potential toxicity of spawning grounds prior to the decline of the allis shad population in spawning grounds in the GGD catchment due to the absence of data during this period.

## 6. Conclusion

The (ms)PAF method, despite its biases, is proving to be a solid tool for assessing and monitoring the quality of water bodies. It has enabled us to quantify toxic pressure and spatio-temporally assess the potential toxic risk to fish in allis shad spawning grounds of the GGD catchment. This approach filled a knowledge gap concerning the chemical contamination of water bodies in this catchment, highlighting a greater potential toxic risk to the spawning grounds of the Garonne, and a greater risk to the development and physiology of fish larvae. A potentially lethal toxic risk to embryos was also not to be overlooked. Thus, a significant potential toxic risk has been demonstrated, particularly for early life stages of fish in the spawning grounds of the Dordogne and Garonne.

The results of this study also corroborate additional work carried out during this internship as part of Sarah Bancel's current thesis, highlighting a high decrease in the probability of survival of allis shad embryos exposed to Garonne water (Fig. 17). However, it is important to note that other factors present in the water, such as parasites and infectious agents, must be taken into account to explain the high mortality observed.

Applying this method to a broader set of quantified environmental values would provide results that are more relevant. To do so, it would be necessary to monitor more chemical compounds and to lower the limits of quantification specific to each molecule. In addition, combining this method with others, such as the SOM (Self-Organizing Map), would enable us to refine the analysis to identify the areas most at risk.
proportion of data from acute to chronic toxicity and/or from NOEC to EC50. Moreover, as mentioned by Jesenska et al. (2013) the use of the toxicity data may also alter the results (use of the most sensitive EC50 or the geometric mean of the EC50s). In addition, physico-chemical parameters such as temperature can modify the toxicity of a chemical compound (Philibert et al., 2023), phenomena that are not included in this method. As observed with calcium and copper, interactions between substances must also be considered. In reality, interactions between substances are more complex, with different modes of toxic action that can generate synergistic effects (increasing additive effects) or antagonistic effects (reducing additive effects). However, at low levels of chemical exposure, these interactions are rare or sufficiently insignificant (Faust et al., 2000). This bias is therefore not considered to be the most important, but must be taken into account.

For ecological risk, using the Th₅% as a reference to protect 95% of species in the fish taxon may distort the analysis of results, as it may not be sufficient to protect the community (Faggiano et al., 2010). Moreover, Pereira et al. (2018) revealed that freshwater communities are influenced in the field by environmental factors and biotic interactions, in addition to the presence of chemical mixtures; this was not taken into account in the method used. Finally, it was not possible to compare the potential toxicity of spawning grounds prior to the decline of the allis shad population in spawning grounds in the GGD catchment due to the absence of data during this period.

## 6. Conclusion

The (ms)PAF method, despite its biases, is proving to be a solid tool for assessing and monitoring the quality of water bodies. It has enabled us to quantify toxic pressure and spatio-temporally assess the potential toxic risk to fish in allis shad spawning grounds of the GGD catchment. This approach filled a knowledge gap concerning the chemical contamination of water bodies in this catchment, highlighting a greater potential toxic risk to the spawning grounds of the Garonne, and a greater risk to the development and physiology of fish larvae. A potentially lethal toxic risk to embryos was also not to be overlooked. Thus, a significant potential toxic risk has been demonstrated, particularly for early life stages of fish in the spawning grounds of the Dordogne and Garonne.

The results of this study also corroborate additional work carried out during this internship as part of Sarah Bancel's current thesis, highlighting a high decrease in the probability of survival of allis shad embryos exposed to Garonne water (Fig. 17). However, it is important to note that other factors present in the water, such as parasites and infectious agents, must be taken into account to explain the high mortality observed.

Applying this method to a broader set of quantified environmental values would provide results that are more relevant. To do so, it would be necessary to monitor more chemical compounds and to lower the limits of quantification specific to each molecule. In addition, combining this method with others, such as the SOM (Self-Organizing Map), would enable us to refine the analysis to identify the areas most at risk.
<figure><img src="image_30.png" /><figcaption>**Figure 17.** Probability of survival of allis shad embryos exposed to Garonne water (red) and tap water (yellow) for batch n°1 (A) and batch n°2 (B) (data from Bancel, in prep.).</figcaption></figure>

This work could help researchers target a few compounds or groups of compounds (e.g. estrone or hormones) to specifically study the effect of these compounds on individuals of allis shad, in order to study the real impact at quantified concentrations in the environment. This would enable managers to take appropriate measures to avoid the potential impacts of such pollution. In addition, the (ms)PAF methodology could even complement the monitoring of water bodies carried out by the SIE by assessing the toxic risk to which species in a particular ecosystem or taxon are subject. In our case, we have assessed the toxic risk to fish in allis shad spawning grounds. However, this assessment could be extended to other spawning grounds to assess the toxic risk within each spawning ground of each diadromous fish species (twoite shad, river or sea lamprey, European sturgeon or Atlantic salmon) in the GGD catchment.

This method could therefore contribute to conservation biology and, in our case, to the conservation of diadromous fish species, potentially impacted by certain substances or mixtures of substances. By targeting one or more problematic chemical compounds, it would be possible to combine management and research to reduce the impact of chemical contaminants by identifying their dynamics (from source through impact to solution). This could also help safeguard ecosystem services threatened by this pollution and contribute to improving water quality in the GGD catchment.
<figure><img src="image_30.png" /><figcaption>**Figure 17.** Probability of survival of allis shad embryos exposed to Garonne water (red) and tap water (yellow) for batch n°1 (A) and batch n°2 (B) (data from Bancel, in prep.).</figcaption></figure>

This work could help researchers target a few compounds or groups of compounds (e.g. estrone or hormones) to specifically study the effect of these compounds on individuals of allis shad, in order to study the real impact at quantified concentrations in the environment. This would enable managers to take appropriate measures to avoid the potential impacts of such pollution. In addition, the (ms)PAF methodology could even complement the monitoring of water bodies carried out by the SIE by assessing the toxic risk to which species in a particular ecosystem or taxon are subject. In our case, we have assessed the toxic risk to fish in allis shad spawning grounds. However, this assessment could be extended to other spawning grounds to assess the toxic risk within each spawning ground of each diadromous fish species (twoite shad, river or sea lamprey, European sturgeon or Atlantic salmon) in the GGD catchment.

This method could therefore contribute to conservation biology and, in our case, to the conservation of diadromous fish species, potentially impacted by certain substances or mixtures of substances. By targeting one or more problematic chemical compounds, it would be possible to combine management and research to reduce the impact of chemical contaminants by identifying their dynamics (from source through impact to solution). This could also help safeguard ecosystem services threatened by this pollution and contribute to improving water quality in the GGD catchment.
7. Bibliography

Acolas, M. L., Véron, V., Jourdan, H., Bégout, M. L., Sabatié, M. R., and Baglinière, J. L. (2006). Upstream migration and reproductive patterns of a population of allis shad in a small river (L'Aulne, Brittany, France). *ICES Journal of Marine Science*. 63, 476-484. doi: 10.1016/j.icesjms.2005.05.022.

Acolas, M.-L., Davail, B., Gonzalez, P., Jean, S., Clérandeau, C., Morin, B., et al. (2020). Health indicators and contaminant levels of a critically endangered species in the Gironde estuary, the European sturgeon. *Environ. Sci. Pollut. Res.* 27, 3726-3745. doi: 10.1007/s11356-019-05139-5.

Aminot, Y. (2013). Etude de l'impact des effluents urbains sur la qualité des eaux de la Garonne estuarienne: application aux composés pharmaceutiques et aux filtres UV. [thesis]. [Bordeaux (France)]: Université de Bordeaux.

Antizar-Ladislao, B. (2008). Environmental levels, toxicity and human exposure to tributyltin (TBT)-contaminated marine environment. A review. *Environment International*. 34, 292-308. doi: 10.1016/j.envint.2007.09.005.

Arrignon, J. (1998). Aménagement piscicole des eaux douces. Paris (France): Tec & Doc Lavoisier.

Audry, S., Schäfer, J., Blanc, G., Bossy, C., and Lavaux, G. (2004). Anthropogenic components of heavy metal (Cd, Zn, Cu, Pb) budgets in the Lot-Garonne fluvial system (France). *Applied Geochemistry*. 19, 769-786. doi: 10.1016/j.apgeochem.2003.10.002.

Aurisano, N., Albizzati, P. F., Hauschild, M., and Fantke, P. (2019). Extrapolation Factors for characterizing Freshwater Ecotoxicity Effects. *Enviro. Toxic. and Chemistry*. 38, 2568-2582. doi: 10.1002/etc.4564.

Baglinière, J.-L., and Elie, P. (2000). Les aloses (*Alosa alosa* et *Alosa fallax* spp.): Écobiologie et variabilité. Paris (France): Cemagref Editions, INRA Editions.

Baglinière, J.-L., Sabatié, M. R., Rochard, E., Alexandrino, P., and Aprahamian, M. W. (2003). The Allis Shad *Alosa alosa*: Biology, Ecology, Range, and Status of Populations. *American Fisheries Society Symposium*. 35, 85-102.

Balon, E. K. (1975). Terminology of Intervals in Fish Development. *J. Fish. Res. Bd. Can.* 32, 1663-1670. doi: 10.1139/f75-196.

Bancel, S. (in prep.). Expérimentation ex situ pour évaluer et comprendre la réponse des jeunes stades de poissons aux conditions environnementales. [thesis]. [Bordeaux (France)]: Université de Bordeaux.

Bardonnet, A., and Jatteau, Ph. (2008). Salinity tolerance in young Allis shad larvae (*Alosa alosa* L.). *Ecol. Freshwater Fish*. 17, 193-197. doi: 10.1111/j.1600-0633.2007.00259.x.

Baumann, L. (2021). Analysis of the ecology of the young stages of allis shad (*Alosa alosa*, Clupeidae): ecological preferenda, sensitivity to environmental pressures and population restoration. [thesis]. [Bordeaux (France)]: Université de Bordeaux.

Beaumelle, L., Della Vedova, C., Beaugelin-Seiller, K., Garnier-Laplace, J., and Gilbin, R. (2017). Ecological risk assessment of mixtures of radiological and chemical stressors: Methodology to implement an msPAF approach. *Environmental Pollution*. 231, 1421-1432. doi: 10.1016/j.envpol.2017.09.003.

Belaud, A., Carette, A., Cassou-Leins, F., and Cassou-Leins, J. J. (2001). Choix des sites de fraie par la grande alose (*Alosa alosa*) en moyenne Garonne. *Bull. Fr. Pêche Piscic.* 362/363, 869-880. doi: 10.1051/kmae:2001024.
7. Bibliography

Acolas, M. L., Véron, V., Jourdan, H., Bégout, M. L., Sabatié, M. R., and Baglinière, J. L. (2006). Upstream migration and reproductive patterns of a population of allis shad in a small river (L'Aulne, Brittany, France). *ICES Journal of Marine Science*. 63, 476-484. doi: 10.1016/j.icesjms.2005.05.022.

Acolas, M.-L., Davail, B., Gonzalez, P., Jean, S., Clérandeau, C., Morin, B., et al. (2020). Health indicators and contaminant levels of a critically endangered species in the Gironde estuary, the European sturgeon. *Environ. Sci. Pollut. Res.* 27, 3726-3745. doi: 10.1007/s11356-019-05139-5.

Aminot, Y. (2013). Etude de l'impact des effluents urbains sur la qualité des eaux de la Garonne estuarienne: application aux composés pharmaceutiques et aux filtres UV. [thesis]. [Bordeaux (France)]: Université de Bordeaux.

Antizar-Ladislao, B. (2008). Environmental levels, toxicity and human exposure to tributyltin (TBT)-contaminated marine environment. A review. *Environment International*. 34, 292-308. doi: 10.1016/j.envint.2007.09.005.

Arrignon, J. (1998). Aménagement piscicole des eaux douces. Paris (France): Tec & Doc Lavoisier.

Audry, S., Schäfer, J., Blanc, G., Bossy, C., and Lavaux, G. (2004). Anthropogenic components of heavy metal (Cd, Zn, Cu, Pb) budgets in the Lot-Garonne fluvial system (France). *Applied Geochemistry*. 19, 769-786. doi: 10.1016/j.apgeochem.2003.10.002.

Aurisano, N., Albizzati, P. F., Hauschild, M., and Fantke, P. (2019). Extrapolation Factors for characterizing Freshwater Ecotoxicity Effects. *Enviro. Toxic. and Chemistry*. 38, 2568-2582. doi: 10.1002/etc.4564.

Baglinière, J.-L., and Elie, P. (2000). Les aloses (*Alosa alosa* et *Alosa fallax* spp.): Écobiologie et variabilité. Paris (France): Cemagref Editions, INRA Editions.

Baglinière, J.-L., Sabatié, M. R., Rochard, E., Alexandrino, P., and Aprahamian, M. W. (2003). The Allis Shad *Alosa alosa*: Biology, Ecology, Range, and Status of Populations. *American Fisheries Society Symposium*. 35, 85-102.

Balon, E. K. (1975). Terminology of Intervals in Fish Development. *J. Fish. Res. Bd. Can.* 32, 1663-1670. doi: 10.1139/f75-196.

Bancel, S. (in prep.). Expérimentation ex situ pour évaluer et comprendre la réponse des jeunes stades de poissons aux conditions environnementales. [thesis]. [Bordeaux (France)]: Université de Bordeaux.

Bardonnet, A., and Jatteau, Ph. (2008). Salinity tolerance in young Allis shad larvae (*Alosa alosa* L.). *Ecol. Freshwater Fish*. 17, 193-197. doi: 10.1111/j.1600-0633.2007.00259.x.

Baumann, L. (2021). Analysis of the ecology of the young stages of allis shad (*Alosa alosa*, Clupeidae): ecological preferenda, sensitivity to environmental pressures and population restoration. [thesis]. [Bordeaux (France)]: Université de Bordeaux.

Beaumelle, L., Della Vedova, C., Beaugelin-Seiller, K., Garnier-Laplace, J., and Gilbin, R. (2017). Ecological risk assessment of mixtures of radiological and chemical stressors: Methodology to implement an msPAF approach. *Environmental Pollution*. 231, 1421-1432. doi: 10.1016/j.envpol.2017.09.003.

Belaud, A., Carette, A., Cassou-Leins, F., and Cassou-Leins, J. J. (2001). Choix des sites de fraie par la grande alose (*Alosa alosa*) en moyenne Garonne. *Bull. Fr. Pêche Piscic.* 362/363, 869-880. doi: 10.1051/kmae:2001024.
Bernard, M. (2018). Déploiement large échelle du POCIS pour l'évaluation de la contamination par les pesticides dans les eaux de surface: apports et complémentarité dans le cadre des réseaux de surveillance du bassin Adour-Garonne. [thesis]. [Bordeaux (France)]: Université de Bordeaux.

Billon, G., Descamps, R., Grare, C., Ouddane, B., and Fischer, J.-C. (2010). Évaluation de la biodisponibilité des métaux dans les sédiments. Available at: https://www.artois-picardie.eaufrance.fr/IMG/pdf/etude_evaluation_biodisponibilite_metaux_2010.pdf [Accessed August 8, 2023].

Blanc, G., Schäfer, J., Audry, S., Bossy, C., Lavaux, G., and Lissalde, J. P. (2006). Le cadmium dans le Lot et la Garonne: sources et transport. *Hydroécol. Appl.* 15, 19-41. doi: 10.1051/hydro:2006005.

Blaya, M., Geffard, O., Jatteau, P., Pierre, M., and Rochard, E. (2022). Embryonic development in allis shad *Alosa alosa*: A baseline for stress studies. *J. Appl. Ichthyol.* 38, 468-472. doi: 10.1111/jai.14336.

Bodin, N., Tapie, N., Le Ménach, K., Chassot, E., Elie, P., Rochard, E., et al. (2014). PCB contamination in fish community from the Gironde Estuary (France): Blast from the past. *Chemosphere*. 98, 66-72. doi: 10.1016/j.chemosphere.2013.10.003.

Boisneau, P., Mennesson-Boisneau, C., and Baglinière, J. L. (1990). Description d'une frayère et comportement de reproduction de la grande Alose (*Alosa alosa* L.) dans le cours supérieur de la Loire. *Bull. Fr. Pêche Piscic.* 316, 15-23. doi: 10.1051/kmae:1990022.

Bonten, L. T. C., Römkens, P. F. A. M., and Brus, D. J. (2008). Contribution of Heavy Metal Leaching from Agricultural Soils to Surface Water Loads. *Environmental Forensics*. 9, 252-257. doi: 10.1080/15275920802122981.

Bouyssonnie, W., and Filloux, D. (2021). Suivi de la reproduction de la grande alose sur la Dordogne. Available at: http://www.migado.fr/wp-content/uploads/2021/05/rapport-AALAD-def.pdf [Accessed July 11, 2023].

Brack, W., Ait-Aissa, S., Burgess, R. M., Busch, W., Creusot, N., Di Paolo, C., et al. (2016). Effect-directed analysis supporting monitoring of aquatic environments - An in-depth overview. *Science of The Total Environment.* 544, 1073-1118. doi: 10.1016/j.scitotenv.2015.11.102.

Bromilow, R. H., Evans, A. A., and Nicholls, P. H. (2003). The influence of lipophilicity and formulation on the distribution of pesticides in laboratory-scale sediment/water systems. *Pest. Manag. Sci.* 59, 238-244. doi: 10.1002/ps.540.

Brungs, W. A. (1969). Chronic Toxicity of Zinc to the Fathead Minnow, *Pimephales promelas* Rafinesque. *Transactions of the American Fisheries Society*. 98, 272-279.

Budzinski, H., Jones, I., Bellocq, J., Piérard, C., and Garrigues, P. (1997). Evaluation of sediment contamination by polycyclic aromatic hydrocarbons in the Gironde estuary. *Marine Chemistry*. 58, 85-97. doi: 10.1016/S0304-4203(97)00028-5.

Bushong, S. J., Hall, L. W., Scott Hall, W., Edward Johnson, W., and Herman, R. L. (1988). Acute toxicity of tributyltin to selected Chesapeake Bay fish and invertebrates. *Water Research*. 22, 1027-1032. doi: 10.1016/0043-1354(88)90150-9.

Canli, E. G., and Canli, M. (2015). Low water conductivity increases the effects of copper on the serum parameters in fish (*Oreochromis niloticus*). *Environmental Toxicology and Pharmacology*. 39, 606-613. doi: 10.1016/j.etap.2014.12.019.

Carafa, R., Faggiano, L., Real, M., Munné, A., Ginebreda, A., Guasch, H., et al. (2011). Water toxicity assessment and spatial pollution patterns identification in a Mediterranean River Basin
Bernard, M. (2018). Déploiement large échelle du POCIS pour l'évaluation de la contamination par les pesticides dans les eaux de surface: apports et complémentarité dans le cadre des réseaux de surveillance du bassin Adour-Garonne. [thesis]. [Bordeaux (France)]: Université de Bordeaux.

Billon, G., Descamps, R., Grare, C., Ouddane, B., and Fischer, J.-C. (2010). Évaluation de la biodisponibilité des métaux dans les sédiments. Available at: https://www.artois-picardie.eaufrance.fr/IMG/pdf/etude_evaluation_biodisponibilite_metaux_2010.pdf [Accessed August 8, 2023].

Blanc, G., Schäfer, J., Audry, S., Bossy, C., Lavaux, G., and Lissalde, J. P. (2006). Le cadmium dans le Lot et la Garonne: sources et transport. *Hydroécol. Appl.* 15, 19-41. doi: 10.1051/hydro:2006005.

Blaya, M., Geffard, O., Jatteau, P., Pierre, M., and Rochard, E. (2022). Embryonic development in allis shad *Alosa alosa*: A baseline for stress studies. *J. Appl. Ichthyol.* 38, 468-472. doi: 10.1111/jai.14336.

Bodin, N., Tapie, N., Le Ménach, K., Chassot, E., Elie, P., Rochard, E., et al. (2014). PCB contamination in fish community from the Gironde Estuary (France): Blast from the past. *Chemosphere*. 98, 66-72. doi: 10.1016/j.chemosphere.2013.10.003.

Boisneau, P., Mennesson-Boisneau, C., and Baglinière, J. L. (1990). Description d'une frayère et comportement de reproduction de la grande Alose (*Alosa alosa* L.) dans le cours supérieur de la Loire. *Bull. Fr. Pêche Piscic.* 316, 15-23. doi: 10.1051/kmae:1990022.

Bonten, L. T. C., Römkens, P. F. A. M., and Brus, D. J. (2008). Contribution of Heavy Metal Leaching from Agricultural Soils to Surface Water Loads. *Environmental Forensics*. 9, 252-257. doi: 10.1080/15275920802122981.

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Geffard, O., Alric, B., François, A., Delorme, N., Noury, P., Chaumot, A., et al. (2019). Lien entre la toxicité, la contamination des milieux aquatiques mesurés chez *Gammarus fossarum* et la perturbation des communautés biologiques. *Lyon-Villeurbanne: Irstea*.

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Warne, S. J. M., and van Dam, R. (2008). NOEC and LOEC data should no longer be generated or used. *Australian Journal of Ecotoxicology.* 14, 1-5.

Wheeler, J. R., Grist, E. P. M., Leung, K. M. Y., Morritt, D., and Crane, M. (2002). Species sensitivity distributions: data and model choice. *Marine Pollution Bulletin.* 45, 192-202. doi: 10.1016/S0025-326X(01)00327-7.
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Zhang, X., Zhu, X., Liu, Y., Hong, X., Huang, J., and Zeng, M. (2015). Acute toxicity of mebendazole, deltamethrin and copper sulphate to *Alosa sapidissima*. *South China Fisheries Science*. 11, 66-71.
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Wu, S. M., Ho, Y.-C., and Shih, M. J. (2007). Effects of Ca2+ or Na+ on metallothionein expression in tilapia larvae (*Oreochromis mossambicus*) exposed to cadmium or copper. *Arch. Environ. Contam. Toxicol.* 52, 229-234. doi: 10.1007/s00244-006-0112-5.

Xu, H., Yang, M., Qiu, W., Pan, C., and Wu, M. (2013). The impact of endocrine-disrupting chemicals on oxidative stress and innate immune response in zebrafish embryos. *Environmental Toxicology* 32, 1793-1799.

Zhang, X., Zhu, X., Liu, Y., Hong, X., Huang, J., and Zeng, M. (2015). Acute toxicity of mebendazole, deltamethrin and copper sulphate to *Alosa sapidissima*. *South China Fisheries Science*. 11, 66-71.
8. Supplementary materials

<table><caption>Supplementary materials #1. Annual average environmental values (quantified + unquantified) for each chemical compound in Garonne and Dordogne spawning grounds.</caption><thead><tr><th>Chemicals</th><th>CAS</th><th>Categories</th><th>Rivers</th><th>2006</th><th>2007</th><th>2008</th><th>2009</th><th>2010</th><th>2011</th><th>2012</th><th>2013</th><th>2014</th><th>2015</th><th>2016</th><th>2017</th><th>2018</th><th>2019</th><th>2020</th><th>2021</th></tr></thead><tbody><tr><td>(-)-Dichlorprop</td><td>15165670</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>2.50E-05</td><td>1.38E-05</td><td>1.00E-05</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td></tr><tr><td>(-)-Dichlorprop</td><td>15165670</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>2.50E-05</td><td>1.38E-05</td><td>1.00E-05</td><td>NA</td><td>NA</td><td>NA</td><td>1.67E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td></tr><tr><td>2.4-D</td><td>94757</td><td>Agrochemicals</td><td>D</td><td>110E-05</td><td>5.00E-06</td><td>1.00E-05</td><td>2.78E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>2.4-D</td><td>94757</td><td>Agrochemicals</td><td>G</td><td>1.68E-05</td><td>1.38E-05</td><td>1.00E-05</td><td>1.92E-05</td><td>1.53E-05</td><td>1.00E-05</td><td>2.53E-05</td><td>1.00E-05</td><td>1.00E-04</td><td>1.67E-05</td><td>6.90E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>2.4-Dichlorophenol</td><td>120832</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>1.13E-08</td><td>NA</td><td>1.05E-04</td><td>NA</td><td>NA</td><td>1.80E-05</td><td>1.13E-07</td><td>1.13E-07</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td></tr><tr><td>2.4-Dichlorophenol</td><td>120832</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>1.13E-08</td><td>NA</td><td>3.27E-05</td><td>5.00E-05</td><td>5.00E-05</td><td>4.21E-05</td><td>2.15E-05</td><td>2.86E-05</td><td>2.86E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td></tr><tr><td>2.4-MCPA</td><td>94746</td><td>Agrochemicals</td><td>D</td><td>1.40E-05</td><td>5.00E-06</td><td>1.00E-05</td><td>7.78E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>6.00E-06</td><td>6.00E-06</td><td>5.75E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>2.4-MCPA</td><td>94746</td><td>Agrochemicals</td><td>G</td><td>1.31E-05</td><td>1.33E-05</td><td>1.00E-05</td><td>1.67E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.17E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>2.6-Diethylaniline</td><td>579668</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>2.6-Diethylaniline</td><td>579668</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>3.4-Dichloroaniline</td><td>95761</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>1.75E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.42E-05</td><td>1.42E-05</td><td>1.42E-05</td><td>1.08E-05</td><td>1.08E-05</td><td>1.08E-05</td></tr><tr><td>3.4-Dichloroaniline</td><td>95761</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>3.80E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>8.13E-06</td><td>8.13E-06</td><td>9.54E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>AMPA</td><td>1066519</td><td>Agrochemicals</td><td>D</td><td>2.50E-05</td><td>2.50E-05</td><td>2.27E-04</td><td>9.00E-05</td><td>2.30E-04</td><td>1.17E-04</td><td>2.50E-05</td><td>1.72E-04</td><td>7.50E-05</td><td>9.33E-05</td><td>4.28E-05</td><td>7.10E-05</td><td>8.00E-05</td><td>7.62E-05</td><td>6.21E-05</td><td>4.62E-05</td></tr><tr><td>AMPA</td><td>1066519</td><td>Agrochemicals</td><td>G</td><td>2.57E-04</td><td>2.50E-05</td><td>1.57E-04</td><td>2.38E-04</td><td>3.33E-04</td><td>1.88E-04</td><td>1.54E-04</td><td>1.62E-04</td><td>1.68E-04</td><td>2.02E-04</td><td>1.70E-04</td><td>2.40E-04</td><td>1.69E-04</td><td>2.07E-04</td><td>1.74E-04</td><td>1.88E-04</td></tr><tr><td>Acetochlor</td><td>34256821</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>3.58E-05</td><td>1.00E-05</td><td>8.34E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>8.34E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>5.83E-06</td><td>6.25E-06</td><td>5.83E-06</td><td>7.55E-06</td><td>3.75E-06</td><td>4.21E-06</td></tr><tr><td>Acetochlor</td><td>34256821</td><td>Agrochemicals</td><td>G</td><td>1.53E-05</td><td>1.29E-04</td><td>3.67E-05</td><td>1.18E-04</td><td>1.00E-05</td><td>4.67E-05</td><td>1.14E-04</td><td>2.24E-05</td><td>1.18E-05</td><td>7.12E-06</td><td>8.13E-06</td><td>8.13E-06</td><td>1.06E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Acetonifen</td><td>74070465</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>8.33E-06</td><td>1.00E-05</td><td>8.34E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>8.34E-06</td><td>1.43E-05</td><td>7.16E-06</td><td>7.16E-06</td><td>1.42E-05</td><td>1.42E-05</td><td>1.46E-05</td><td>1.08E-05</td><td>1.42E-05</td><td>1.46E-05</td></tr><tr><td>Acetonifen</td><td>74070465</td><td>Agrochemicals</td><td>G</td><td>1.06E-05</td><td>2.07E-05</td><td>1.38E-05</td><td>1.22E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.06E-06</td><td>2.46E-05</td><td>3.28E-05</td><td>1.44E-05</td><td>2.90E-05</td><td>2.75E-05</td><td>2.26E-05</td><td>1.00E-05</td><td>2.28E-05</td><td>1.00E-05</td></tr><tr><td>Alachlor</td><td>15972608</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>3.69E-05</td><td>1.00E-05</td><td>1.09E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.82E-06</td><td>2.87E-06</td><td>2.87E-06</td><td>5.19E-06</td><td>5.83E-06</td><td>5.44E-06</td><td>7.55E-06</td><td>5.83E-06</td><td>5.37E-06</td><td>5.37E-06</td></tr><tr><td>Alachlor</td><td>15972608</td><td>Agrochemicals</td><td>G</td><td>1.67E-05</td><td>4.55E-05</td><td>1.00E-05</td><td>6.69E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>9.28E-06</td><td>6.88E-06</td><td>7.24E-06</td><td>9.63E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.32E-05</td></tr><tr><td>Alachlor ESA</td><td>142363539</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Alachlor ESA</td><td>142363539</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Aminotriazole</td><td>61825</td><td>Agrochemicals</td><td>D</td><td>2.50E-05</td><td>1.00E-05</td><td>5.00E-05</td><td>4.00E-05</td><td>5.00E-05</td><td>5.00E-05</td><td>5.00E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>4.58E-05</td><td>3.00E-05</td><td>3.00E-05</td><td>2.88E-05</td><td>1.90E-05</td><td>3.73E-05</td><td>2.50E-05</td></tr><tr><td>Aminotriazole</td><td>61825</td><td>Agrochemicals</td><td>G</td><td>5.93E-05</td><td>1.00E-05</td><td>1.17E-04</td><td>1.10E-04</td><td>5.00E-05</td><td>5.00E-05</td><td>5.00E-05</td><td>4.58E-05</td><td>4.08E-05</td><td>4.72E-05</td><td>4.25E-05</td><td>4.25E-05</td><td>2.85E-05</td><td>1.93E-05</td><td>1.50E-05</td><td>1.50E-05</td></tr><tr><td>Anthraquinone</td><td>84651</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>3.01E-08</td><td>2.88E-06</td><td>4.67E-08</td><td>1.04E-07</td><td>1.64E-07</td><td>2.11E-06</td></tr><tr><td>Anthraquinone</td><td>84651</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>6.81E-06</td><td>7.72E-06</td><td>4.02E-06</td><td>3.76E-06</td><td>6.10E-06</td><td>5.45E-06</td></tr><tr><td>Atrazine</td><td>1912249</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>3.23E-05</td><td>5.00E-06</td><td>4.68E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>5.12E-06</td><td>2.87E-06</td><td>2.87E-06</td><td>5.19E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Atrazine</td><td>1912249</td><td>Agrochemicals</td><td>G</td><td>1.63E-05</td><td>1.32E-05</td><td>1.13E-05</td><td>7.59E-06</td><td>4.33E-05</td><td>1.00E-05</td><td>9.28E-06</td><td>6.88E-06</td><td>1.22E-05</td><td>9.63E-06</td><td>6.40E-06</td><td>5.00E-06</td><td>6.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>6.40E-06</td></tr><tr><td>Azoxystrobin</td><td>131860338</td><td>Agrochemicals</td><td>D</td><td>2.50E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Azoxystrobin</td><td>131860338</td><td>Agrochemicals</td><td>G</td><td>2.50E-05</td><td>1.47E-05</td><td>6.67E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.33E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>6.00E-06</td><td>5.75E-06</td><td>1.00E-05</td><td>1.30E-05</td></tr><tr><td>Bentazon</td><td>25057890</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Bentazon</td><td>25057890</td><td>Agrochemicals</td><td>G</td><td>2.23E-05</td><td>3.50E-05</td><td>1.33E-05</td><td>2.16E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>3.33E-05</td><td>3.00E-05</td><td>2.67E-05</td><td>1.64E-04</td><td>3.67E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.97E-05</td></tr><tr><td>Biphenyl</td><td>92524</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>2.08E-05</td><td>5.00E-05</td><td>2.67E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.41E-06</td><td>7.15E-06</td><td>7.15E-06</td><td>7.15E-06</td><td>7.15E-06</td><td>2.50E-05</td><td>5.38E-06</td><td>5.38E-06</td><td>5.23E-06</td><td>5.23E-06</td></tr><tr><td>Biphenyl</td><td>92524</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>2.50E-05</td><td>5.00E-05</td><td>2.36E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.14E-06</td><td>1.35E-05</td><td>1.44E-05</td><td>1.44E-05</td><td>2.23E-05</td><td>1.93E-05</td><td>1.88E-05</td><td>1.78E-05</td><td>1.93E-05</td><td>1.78E-05</td></tr><tr><td>Boscald</td><td>188425856</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Boscald</td><td>188425856</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.70E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Carbaryl</td><td>63252</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Carbaryl</td><td>63252</td><td>Agrochemicals</td><td>G</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Carbendazim</td><td>10605217</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.33E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.28E-06</td><td>7.61E-06</td><td>5.00E-06</td><td>4.18E-06</td><td>3.07E-06</td><td>3.07E-06</td></tr><tr><td>Carbamide</td><td>16118493</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>7.38E-06</td><td>6.69E-06</td><td>1.51E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Carbamide</td><td>16118493</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Carbofuran</td><td>1563662</td><td>Agrochemicals</td><td>G</td><td>1.57E-05</td><td>4.03E-06</td><td>9.17E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Carbofuran</td><td>1563662</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Chloridazon</td><td>1698608</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Chloridazon</td><td>1698608</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Chlortoluron</td><td>15545489</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>6.25E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>5.49E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>6.00E-06</td><td>6.00E-06</td><td>5.75E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Chlortoluron</td><td>15545489</td><td>Agrochemicals</td><td>D</td><td>4.70E-05</td><td>4.10E-05</td><td>1.00E-05</td><td>6.67E-06</td><td>1.00E-05</td><td>1.93E-05</td><td>7.00E-05</td><td>6.79E-05</td><td>3.52E-05</td><td>3.71E-05</td><td>1.43E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Clopyralid</td><td>1702176</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Clopyralid</td><td>1702176</td><td>Agrochemicals</td><td>G</td><td>8.67E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>1.50E-05</td><td>1.50E-05</td><td>1.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Cyanazine</td><td>21725462</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Cyanazine</td><td>21725462</td><td>Agrochemicals</td><td>G</td><td>6.67E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Cyazofamid</td><td>120116883</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Cyazofamid</td><td>120116883</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>7.50E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Cypermethrin</td><td>52315078</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>5.91E-06</td><td>5.83E-06</td><td>1.04E-05</td><td>9.18E-06</td><td>5.83E-06</td><td>5.37E-06</td></tr><tr><td>Cypermethrin</td><td>52315078</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.37E-06</td><td>5.37E-06</td></tr><tr><td>Deethylatrazine</td><td>6190654</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>4.17E-06</td><td>6.00E-05</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>7.78E-06</td><td>1.00E-05</td><td>5.00E-06</td><td>2.00E-05</td><td>7.50E-06</td><td>1.50E-05</td><td>8.00E-06</td><td>5.82E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Deethylatrazine</td><td>6190654</td><td>Agrochemicals</td><td>D</td><td>1.50E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.58E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.75E-06</td><td>7.50E-06</td><td>1.00E-05</td><td>6.75E-06</td><td>6.50E-06</td><td>6.50E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Dicamba</td><td>1918009</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.50E-05</td><td>2.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.60E-05</td><td>1.38E-05</td><td>1.25E-05</td><td>2.25E-05</td><td>2.08E-05</td><td>2.12E-05</td></tr><tr><td>Dicamba</td><td>1918009</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.00E-05</td><td>2.00E-05</td><td>1.00E-05</td><td>1.31E-05</td><td>3.13E-05</td><td>3.44E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Dichlorprop</td><td>120365</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>8.33E-06</td><td>1.30E-05</td><td>7.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>7.01E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>1.00E-05</td><td>5.30E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Dichlorprop</td><td>120365</td><td>Agrochemicals</td><td>G</td><td>6.67E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>2.47E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.94E-06</td><td>1.20E-05</td><td>7.13E-06</td><td>2.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Diffulfenican</td><td>83164334</td><td>Agrochemicals</td><td>D</td><td>2.50E-05</td><td>3.50E-05</td><td>1.00E-05</td><td>8.34E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.08E-05</td><td>2.89E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.09E-06</td><td>1.09E-06</td><td>1.09E-06</td></tr><tr><td>Diffulfenican</td><td>83164334</td><td>Agrochemicals</td><td>G</td><td>2.50E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.35E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>1.39E-05</td><td>5.62E-06</td><td>5.98E-06</td><td>5.97E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>3.58E-06</td><td>3.86E-06</td><td>3.58E-06</td><td>3.58E-06</td></tr></tbody></table>
## 8. Supplementary materials

<table><caption>Supplementary materials #1. Annual average environmental values (quantified + unquantified) for each chemical compound in Garonne and Dordogne spawning grounds.</caption><thead><tr><th>Chemicals</th><th>CAS</th><th>Categories</th><th>Rivers</th><th>2006</th><th>2007</th><th>2008</th><th>2009</th><th>2010</th><th>2011</th><th>2012</th><th>2013</th><th>2014</th><th>2015</th><th>2016</th><th>2017</th><th>2018</th><th>2019</th><th>2020</th><th>2021</th></tr></thead><tbody><tr><td>(-)-Dichlorprop</td><td>15165670</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>2.50E-05</td><td>1.38E-05</td><td>1.00E-05</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td></tr><tr><td>(-)-Dichlorprop</td><td>15165670</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>2.50E-05</td><td>1.38E-05</td><td>1.00E-05</td><td>NA</td><td>NA</td><td>NA</td><td>1.67E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td></tr><tr><td>2.4-D</td><td>94757</td><td>Agrochemicals</td><td>D</td><td>110E-05</td><td>5.00E-06</td><td>1.00E-05</td><td>2.78E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>2.4-D</td><td>94757</td><td>Agrochemicals</td><td>G</td><td>1.68E-05</td><td>1.38E-05</td><td>1.00E-05</td><td>1.92E-05</td><td>1.53E-05</td><td>1.00E-05</td><td>2.53E-05</td><td>1.00E-05</td><td>1.00E-04</td><td>1.67E-05</td><td>6.90E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>2.4-Dichlorophenol</td><td>120832</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>1.13E-08</td><td>NA</td><td>1.05E-04</td><td>NA</td><td>NA</td><td>1.80E-05</td><td>1.13E-07</td><td>1.13E-07</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td></tr><tr><td>2.4-Dichlorophenol</td><td>120832</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>1.13E-08</td><td>NA</td><td>3.27E-05</td><td>5.00E-05</td><td>5.00E-05</td><td>4.21E-05</td><td>2.15E-05</td><td>2.86E-05</td><td>2.86E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td></tr><tr><td>2.4-MCPA</td><td>94746</td><td>Agrochemicals</td><td>D</td><td>1.40E-05</td><td>5.00E-06</td><td>1.00E-05</td><td>7.78E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>6.00E-06</td><td>6.00E-06</td><td>5.75E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>2.4-MCPA</td><td>94746</td><td>Agrochemicals</td><td>G</td><td>1.31E-05</td><td>1.33E-05</td><td>1.00E-05</td><td>1.67E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.17E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>2.6-Diethylaniline</td><td>579668</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>2.6-Diethylaniline</td><td>579668</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>3.4-Dichloroaniline</td><td>95761</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>1.75E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.42E-05</td><td>1.42E-05</td><td>1.42E-05</td><td>1.08E-05</td><td>1.08E-05</td><td>1.42E-05</td></tr><tr><td>3.4-Dichloroaniline</td><td>95761</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>3.80E-05</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>8.13E-06</td><td>8.13E-06</td><td>9.54E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>AMPA</td><td>1066519</td><td>Agrochemicals</td><td>D</td><td>2.50E-05</td><td>2.50E-05</td><td>2.27E-04</td><td>9.00E-05</td><td>2.30E-04</td><td>1.17E-04</td><td>2.50E-05</td><td>1.72E-04</td><td>7.50E-05</td><td>9.33E-05</td><td>4.28E-05</td><td>7.10E-05</td><td>8.00E-05</td><td>7.62E-05</td><td>6.21E-05</td><td>4.62E-05</td></tr><tr><td>AMPA</td><td>1066519</td><td>Agrochemicals</td><td>G</td><td>2.57E-04</td><td>2.50E-05</td><td>1.57E-04</td><td>2.38E-04</td><td>3.33E-04</td><td>1.88E-04</td><td>1.54E-04</td><td>1.62E-04</td><td>1.68E-04</td><td>2.02E-04</td><td>1.70E-04</td><td>2.40E-04</td><td>1.69E-04</td><td>2.07E-04</td><td>1.74E-04</td><td>1.88E-04</td></tr><tr><td>Acetochlor</td><td>34256821</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>3.58E-05</td><td>1.00E-05</td><td>8.34E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>8.34E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>5.83E-06</td><td>6.25E-06</td><td>5.83E-06</td><td>7.55E-06</td><td>3.75E-06</td><td>4.21E-06</td></tr><tr><td>Acetochlor</td><td>34256821</td><td>Agrochemicals</td><td>G</td><td>1.53E-05</td><td>1.29E-04</td><td>3.67E-05</td><td>1.18E-04</td><td>1.00E-05</td><td>4.67E-05</td><td>1.14E-04</td><td>2.24E-05</td><td>1.18E-05</td><td>7.12E-06</td><td>8.13E-06</td><td>8.13E-06</td><td>1.06E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Acetonifen</td><td>74070465</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>8.33E-06</td><td>1.00E-05</td><td>8.34E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>8.34E-06</td><td>1.43E-05</td><td>7.16E-06</td><td>7.16E-06</td><td>1.42E-05</td><td>1.42E-05</td><td>1.46E-05</td><td>1.08E-05</td><td>1.42E-05</td><td>1.46E-05</td></tr><tr><td>Acetonifen</td><td>74070465</td><td>Agrochemicals</td><td>G</td><td>1.06E-05</td><td>2.07E-05</td><td>1.38E-05</td><td>1.22E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.06E-06</td><td>2.46E-05</td><td>3.28E-05</td><td>1.44E-05</td><td>2.90E-05</td><td>2.75E-05</td><td>2.26E-05</td><td>1.00E-05</td><td>2.28E-05</td><td>1.00E-05</td></tr><tr><td>Alachlor</td><td>15972608</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>3.69E-05</td><td>1.00E-05</td><td>1.09E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.82E-06</td><td>2.87E-06</td><td>2.87E-06</td><td>5.19E-06</td><td>5.83E-06</td><td>5.44E-06</td><td>7.55E-06</td><td>5.83E-06</td><td>5.37E-06</td><td>5.37E-06</td></tr><tr><td>Alachlor</td><td>15972608</td><td>Agrochemicals</td><td>G</td><td>1.67E-05</td><td>4.55E-05</td><td>1.00E-05</td><td>6.69E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>9.28E-06</td><td>6.88E-06</td><td>7.24E-06</td><td>9.63E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.32E-05</td></tr><tr><td>Alachlor ESA</td><td>142363539</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Alachlor ESA</td><td>142363539</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Aminotriazole</td><td>61825</td><td>Agrochemicals</td><td>D</td><td>2.50E-05</td><td>1.00E-05</td><td>5.00E-05</td><td>4.00E-05</td><td>5.00E-05</td><td>5.00E-05</td><td>5.00E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>4.58E-05</td><td>3.00E-05</td><td>3.00E-05</td><td>2.88E-05</td><td>1.90E-05</td><td>3.73E-05</td><td>2.50E-05</td></tr><tr><td>Aminotriazole</td><td>61825</td><td>Agrochemicals</td><td>G</td><td>5.93E-05</td><td>1.00E-05</td><td>1.17E-04</td><td>1.10E-04</td><td>5.00E-05</td><td>5.00E-05</td><td>5.00E-05</td><td>4.58E-05</td><td>4.08E-05</td><td>4.72E-05</td><td>4.25E-05</td><td>4.25E-05</td><td>2.85E-05</td><td>1.93E-05</td><td>1.50E-05</td><td>1.50E-05</td></tr><tr><td>Anthraquinone</td><td>84651</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>3.01E-08</td><td>2.88E-06</td><td>4.67E-08</td><td>1.04E-07</td><td>1.64E-07</td><td>2.11E-06</td></tr><tr><td>Anthraquinone</td><td>84651</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>6.81E-06</td><td>7.72E-06</td><td>4.02E-06</td><td>3.76E-06</td><td>6.10E-06</td><td>5.45E-06</td></tr><tr><td>Atrazine</td><td>1912249</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>3.23E-05</td><td>5.00E-06</td><td>4.68E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>5.12E-06</td><td>2.87E-06</td><td>2.87E-06</td><td>5.19E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Atrazine</td><td>1912249</td><td>Agrochemicals</td><td>G</td><td>1.63E-05</td><td>1.32E-05</td><td>1.13E-05</td><td>7.59E-06</td><td>4.33E-05</td><td>1.00E-05</td><td>9.28E-06</td><td>6.88E-06</td><td>1.22E-05</td><td>9.63E-06</td><td>6.40E-06</td><td>5.00E-06</td><td>6.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>6.40E-06</td></tr><tr><td>Azoxystrobin</td><td>131860338</td><td>Agrochemicals</td><td>D</td><td>2.50E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Azoxystrobin</td><td>131860338</td><td>Agrochemicals</td><td>G</td><td>2.50E-05</td><td>1.47E-05</td><td>6.67E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.33E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>6.00E-06</td><td>5.75E-06</td><td>1.00E-05</td><td>1.30E-05</td></tr><tr><td>Bentazon</td><td>25057890</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Bentazon</td><td>25057890</td><td>Agrochemicals</td><td>G</td><td>2.23E-05</td><td>3.50E-05</td><td>1.33E-05</td><td>2.16E-05</td><td>1.00E-05</td><td>3.33E-05</td><td>3.00E-05</td><td>2.67E-05</td><td>1.64E-04</td><td>3.67E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.97E-05</td></tr><tr><td>Biphenyl</td><td>92524</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>2.08E-05</td><td>5.00E-05</td><td>2.67E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.41E-06</td><td>7.15E-06</td><td>7.15E-06</td><td>7.15E-06</td><td>7.15E-06</td><td>2.50E-05</td><td>5.38E-06</td><td>5.38E-06</td><td>5.23E-06</td><td>5.23E-06</td></tr><tr><td>Biphenyl</td><td>92524</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>2.50E-05</td><td>5.00E-05</td><td>2.36E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.14E-06</td><td>1.35E-05</td><td>1.44E-05</td><td>1.44E-05</td><td>2.23E-05</td><td>1.93E-05</td><td>1.88E-05</td><td>1.78E-05</td><td>1.93E-05</td><td>1.78E-05</td></tr><tr><td>Boscald</td><td>188425856</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Boscald</td><td>188425856</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.70E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Carbaryl</td><td>63252</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Carbaryl</td><td>63252</td><td>Agrochemicals</td><td>G</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Carbendazim</td><td>10605217</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.33E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.28E-06</td><td>7.61E-06</td><td>5.00E-06</td><td>4.18E-06</td><td>3.07E-06</td><td>3.07E-06</td></tr><tr><td>Carbamide</td><td>16118493</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>7.38E-06</td><td>6.69E-06</td><td>1.51E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Carbamide</td><td>16118493</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Carbofuran</td><td>1563662</td><td>Agrochemicals</td><td>G</td><td>1.57E-05</td><td>4.03E-05</td><td>9.17E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Carbofuran</td><td>1563662</td><td>Agrochemicals</td><td>D</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Chloridazon</td><td>1698608</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Chloridazon</td><td>1698608</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Chlortoluron</td><td>15545489</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>6.25E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>5.49E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>6.00E-06</td><td>6.00E-06</td><td>5.75E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Chlortoluron</td><td>15545489</td><td>Agrochemicals</td><td>D</td><td>4.70E-05</td><td>4.10E-05</td><td>1.00E-05</td><td>6.67E-06</td><td>1.00E-05</td><td>1.93E-05</td><td>7.00E-05</td><td>6.79E-05</td><td>3.52E-05</td><td>3.71E-05</td><td>1.43E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Clopyralid</td><td>1702176</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Clopyralid</td><td>1702176</td><td>Agrochemicals</td><td>G</td><td>8.67E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>1.50E-05</td><td>1.50E-05</td><td>1.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Cyanazine</td><td>21725462</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Cyanazine</td><td>21725462</td><td>Agrochemicals</td><td>G</td><td>6.67E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Cyazofamid</td><td>120116883</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Cyazofamid</td><td>120116883</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>7.50E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Cypermethrin</td><td>52315078</td><td>Agrochemicals</td><td>D</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>5.91E-06</td><td>5.83E-06</td><td>1.04E-05</td><td>9.18E-06</td><td>5.83E-06</td><td>5.37E-06</td></tr><tr><td>Cypermethrin</td><td>52315078</td><td>Agrochemicals</td><td>G</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>NA</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>5.00E-06</td><td>5.37E-06</td><td>5.37E-06</td></tr><tr><td>Deethylatrazine</td><td>6190654</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>4.17E-06</td><td>6.00E-05</td><td>5.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>7.78E-06</td><td>1.00E-05</td><td>5.00E-06</td><td>2.00E-05</td><td>7.50E-06</td><td>1.50E-05</td><td>8.00E-06</td><td>5.82E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Deethylatrazine</td><td>6190654</td><td>Agrochemicals</td><td>D</td><td>1.50E-05</td><td>5.00E-06</td><td>5.00E-06</td><td>1.58E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.75E-06</td><td>7.50E-06</td><td>1.00E-05</td><td>6.75E-06</td><td>6.50E-06</td><td>6.50E-06</td><td>6.50E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Dicamba</td><td>1918009</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.50E-05</td><td>2.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.60E-05</td><td>1.38E-05</td><td>1.25E-05</td><td>2.25E-05</td><td>2.08E-05</td><td>2.12E-05</td></tr><tr><td>Dicamba</td><td>1918009</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>2.00E-05</td><td>2.00E-05</td><td>1.00E-05</td><td>1.31E-05</td><td>3.13E-05</td><td>3.44E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td><td>2.50E-05</td></tr><tr><td>Dichlorprop</td><td>120365</td><td>Agrochemicals</td><td>D</td><td>5.00E-06</td><td>8.33E-06</td><td>1.30E-05</td><td>7.00E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>7.01E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>1.00E-05</td><td>5.30E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Dichlorprop</td><td>120365</td><td>Agrochemicals</td><td>G</td><td>6.67E-06</td><td>1.00E-05</td><td>1.00E-05</td><td>2.47E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.94E-06</td><td>1.20E-05</td><td>7.13E-06</td><td>2.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>1.00E-05</td></tr><tr><td>Difflufenican</td><td>83164334</td><td>Agrochemicals</td><td>D</td><td>2.50E-05</td><td>3.50E-05</td><td>1.00E-05</td><td>8.34E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>2.08E-05</td><td>2.89E-06</td><td>2.89E-06</td><td>2.89E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>5.00E-06</td></tr><tr><td>Difflufenican</td><td>83164334</td><td>Agrochemicals</td><td>G</td><td>2.50E-05</td><td>1.00E-05</td><td>1.00E-05</td><td>8.35E-06</td><td>2.50E-05</td><td>2.50E-05</td><td>1.39E-05</td><td>5.62E-06</td><td>5.98E-06</td><td>5.97E-06</td><td>5.00E-06</td><td>5.00E-06</td><td>3.58E-06</td><td>3.86E-06</td><td>3.58E-06</td><td>3.58E-06</td></tr></tbody></table>