Chemical Survey and Risk Assessment of 56 Pesticides in the Sado River Estuary (Iberian Peninsula, Portugal)
Abstract
:1. Introduction
2. Materials and Methods
2.1. Study Area
2.2. Water Collection
2.3. Physicochemical Parameters
2.4. Materials and Chemicals for GC-MS/MS Analyses
2.5. Sample Preparation
2.6. Quantitative Analysis
2.7. Pesticide Hazard Assessment
2.8. In Vivo Toxicity Tests
2.9. Data Presentation and Statistical Analyses
3. Results
3.1. Pesticide Concentrations in the Sado Surface Waters
3.2. European Regulations for Pesticides
3.3. Evaluation of the Aquatic Hazard of Pesticide Mixtures
3.4. In Vivo Toxicity Test
3.5. Physicochemical Parameters
4. Discussion
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Fungicides | MDL (ng/L) | Frequency | Environmental Levels (ng/L) ± Mean (SD) | |||
---|---|---|---|---|---|---|
(%) | Spring | Summer | Autumn | Winter | ||
Azoxystrobin | 2.8 | 100 | 342.4 ± 462.2 | 265.1 ± 386.6 | 315.3 ± 536.6 | 649.9 ± 1466 |
Difenoconazole | 2.0 | 100 | 6170 ± 14,409 | 262.7 ± 485.5 | 268.4 ± 725.2 | 620.3 ± 1202 |
HCB | 2.1 | 59 | 3.6 ± 4.8 | 2.6 ± 2.1 | 2.3 ± 2.1 | 3.9 ± 6.6 |
PCB | 2.7 | 89 | 16.7 ± 17.6 | 17.8 ± 26.6 | 11.8 ± 19.8 | 6.9 ± 5.4 |
Procymidone | 2.0 | 100 | 159.4 ± 360.1 | 355.5 ± 928.6 | 409.6 ± 967.8 | 915.2 ± 2171 |
Tebuconazole | 1.8 | 100 | 238.4 ± 388.2 | 675.6 ± 1645 | 509.2 ± 1209 | 388.8 ± 829.4 |
% Frequency > MDL | 91 | |||||
Fungicides (Σaverage) | 6930 ± 5785 | 1579 ± 623 | 1517 ± 493 | 2585 ± 851 | ||
Herbicides | MDL (ng/L) | Frequency (%) | Environmental Levels (ng/L) ± Mean (SD) | |||
Spring | Summer | Autumn | Winter | |||
Alachlor | 1.5 | 87 | 8.0 ± 11.5 | 6.6 ± 11.9 | 7.6 ± 11.9 | 5.7 ± 8.5 |
Atrazine | 2.1 | 68 | 11.4 ± 12.3 | 10.8 ± 9.0 | 7.4 ± 9.0 | 7.0 ± 8.5 |
Atrazine-desethyl | 1.6 | 100 | 51.9 ± 41.1 | 57.3 ± 48.1 | 56.1 ± 48.1 | 37.2 ± 19.7 |
Cyanazine | 1.9 | 100 | 95.0 ± 89.5 | 53.6 ± 74.8 | 61.5 ± 74.8 | 69.8 ± 92.3 |
Cyhalofop-butyl | 2.9 | 98 | 471.3 ± 737.1 | 535.0 ± 790.9 | 406.4 ± 790.9 | 547.4 ± 1131 |
Metolachlor | 3.1 | 23 | 3.1 ± 1.6 | 2.7 ± 1.9 | 2.9 ± 1.9 | 4.9 ± 7.7 |
Metribuzin | 1.8 | 100 | 253.3 ± 179.8 | 58.6 ± 55.3 | 60.0 ± 55.3 | 157.5 ±283.0 |
Pendimethalin | 1.4 | 100 | 5.8 ± 3.2 | 6.0 ± 7.8 | 7.2 ± 7.8 | 5.3 ± 4.4 |
Propazine | 1.7 | 100 | 161.1 ± 218.2 | 45.4 ± 44.9 | 45.0 ± 44.9 | 54.7 ± 79.4 |
Propyzamide | 1.8 | 100 | 57.5 ± 66.5 | 25.2 ± 35.3 | 30.9 ± 35.3 | 34.0 ± 39.6 |
Simazine | 2.8 | 100 | 43.1 ± 52.1 | 37.9 ± 26.9 | 27.0 ± 26.9 | 43.5 ± 78.9 |
Simetryn | 1.8 | 100 | 21.2 ± 22.6 | 20.1 ± 25.6 | 20.5 ± 25.6 | 23.2 ± 32.2 |
Terbuthylazine | 1.5 | 100 | 202.0 ± 264.1 | 50.3 ± 60.0 | 56.8 ± 60.0 | 54.6 ± 68.0 |
Terbutryn | 2.0 | 94 | 10.9 ± 14.2 | 8.8 ± 12.9 | 9.8 ± 12.9 | 10.8 ± 19.7 |
Trifluralin | 2.2 | 42 | 3.1 ± 2.0 | 2.7 ± 2.0 | 3.0 ± 2.0 | 4.0 ± 5.7 |
% Frequency > MDL | 87 | |||||
Herbicides (Σaverage) | 1399 ± 192 | 921 ± 198 | 802 ± 198 | 1060 ± 287 | ||
Insecticides | MDL (ng/L) | Frequency (%) | Environmental Levels (ng/L) ± Mean (SD) | |||
Spring | Summer | Autumn | Winter | |||
Aldrin | 2.5 | 58 | 138.2 ± 283.9 | 91.1 ± 200.4 | 59.5 ± 102.4 | 280.1 ± 821.3 |
Azinphos-methyl | 2.8 | 100 | 3082 ± 7649 | 2778 ± 7515 | 1673 ± 3839 | 172.2 ± 149.9 |
Chlordane γ | 1.8 | 47 | 76.9 ± 189.9 | 41.0 ± 98.0 | 18.8 ± 31.7 | 9.6 ± 16.9 |
Chlorpyriphos | 2.3 | 100 | 115.1 ± 286.1 | 92.3 ± 264.2 | 40.5 ± 82.6 | 375.8 ± 1100.6 |
Chlorfenvinphos | 1.8 | 75 | 141.5 ± 338.9 | 65.2 ± 149.1 | 64.4 ± 132.5 | 349.5 ± 994.4 |
Cyfluthrine | 1.9 | 100 | 1643 ± 4381 | 865.6 ± 2255 | 402.5 ± 880.0 | 3574 ± 10,439 |
Cyhalothrin-λ | 2.1 | 100 | 558.2 ± 1512 | 348.7 ± 1193 | 124.3 ± 292.1 | 489.4 ± 1420 |
Cypermethrin-α | 1.9 | 100 | 687.0 ± 1833 | 319.2 ± 884.1 | 218.7 ± 495.4 | 689.9 ± 1980 |
DDD | 1.9 | 92 | 152.5 ± 401.4 | 72.8 ± 200.8 | 33.0 ± 69.9 | 710.5 ± 2100 |
DDE | 1.6 | 53 | 37.1 ± 94.0 | 24.6 ± 58.1 | 19.3 ± 44.1 | 322.3 ± 955.0 |
DDT | 2.4 | 72 | 518.3 ± 1218 | 79.9 ± 216.1 | 71.1 ± 185.9 | 470.0 ± 1357 |
Deltametrin | 2.2 | 100 | 659.8 ± 1608 | 508.2 ± 1375 | 266.1 ± 543.0 | 1062 ± 3026 |
Diazinon | 1.7 | 100 | 327.5 ± 478.7 | 222.1 ± 265.8 | 197.4 ± 281.2 | 447.9 ± 814.6 |
Dichlorvos | 2.4 | 100 | 67.1 ± 60.7 | 60.3 ± 101.4 | 62.0 ± 74.1 | 33.0 ± 23.4 |
Dieldrin | 2.0 | 100 | 153.7 ± 395.3 | 132.7 ± 286.3 | 163.4 ± 293.7 | 869.7 ± 2155.7 |
Dimethoate | 2.6 | 100 | 349.0 ± 531.7 | 407.2 ± 707.7 | 441.9 ± 403.7 | 581.4 ± 971.6 |
Endosulfan-α | 1.6 | 100 | 394.5 ± 976.3 | 214.8 ± 526.6 | 193.3 ± 440.2 | 693.4 ± 1990 |
Endosulfan-β | 2.2 | 70 | 175.7 ± 361.1 | 82.8 ± 161.6 | 55.7 ± 100.8 | 377.0 ± 1035 |
Endosulfan-sulphate | 2.1 | 100 | 1378 ± 2114 | 410.9 ± 1079 | 226.0 ± 532.0 | 272.4 ± 437.9 |
Endrin | 2.0 | 100 | 368.8 ± 923.7 | 353.3 ± 1119 | 134.0 ± 251.6 | 1279 ± 3689 |
Fenamiphos | 2.5 | 100 | 1466 ± 3413 | 2032 ± 6380 | 855.3 ± 1821 | 4986 ± 14,321 |
Fenitrothion | 1.8 | 98 | 12.6 ± 5.6 | 17.4 ± 19.7 | 15.3 ± 21.7 | 15.2 ± 17.2 |
Fonofos | 1.4 | 100 | 61.3 ± 36.4 | 104.7 ± 131.1 | 94.7 ± 85.6 | 92.8 ± 105.1 |
Heptachlor | 2.3 | 51 | 5.0 ± 4.6 | 4.8 ± 4.5 | 5.2 ± 6.9 | 36.6 ± 89.9 |
Heptachlor-epoxide | 1.6 | 60 | 193.2 ± 347.8 | 46.5 ± 109.5 | 19.0 ± 31.3 | 76.7 ± 139.6 |
HCCP | 1.1 | 0 | 0.8 ± 0.0 | 0.8 ± 0.0 | 0.8 ± 0.0 | 0.8 ± 0.0 |
Lindane | 2.3 | 85 | 47.5 ± 68.8 | 8.8 ± 7.7 | 7.5 ± 8.2 | 12.8 ± 16.5 |
Malathion | 3.1 | 100 | 27.5 ± 21.5 | 18.0 ± 20.3 | 22.1 ± 27.8 | 27.3 ± 36.8 |
Methoxychlor | 1.3 | 100 | 401.6 ± 712.9 | 257.6 ± 651.8 | 67.6 ± 165.8 | 265.3 ± 608.2 |
Mirex | 1.8 | 96 | 733.8 ± 2034 | 228.2 ± 785.7 | 125.5 ± 314.5 | 554.4 ± 1621 |
Parathion-ethyl | 2.6 | 64 | 9.2 ± 7.8 | 8.1 ± 14.0 | 8.7 ± 12.8 | 8.2 ± 13.8 |
Parathion-methyl | 2.0 | 74 | 25.8 ± 21.8 | 24.1 ± 25.6 | 22.8 ± 18.8 | 16.9 ± 13.0 |
Phosmet | 2.4 | 87 | 55.1 ± 28.7 | 84.4 ± 93.0 | 54.5 ± 55.9 | 54.2 ± 144.5 |
Pirimicarb | 1.5 | 100 | 104.0 ± 89.9 | 77.3 ± 70.9 | 115.7 ± 156.1 | 147.1 ± 234.5 |
Tetrachlorvinphos | 1.2 | 100 | 563.1 ± 1462 | 417.1 ± 1123 | 179.2 ± 389.4 | 621.2 ± 1739 |
% Frequency > MDL | 85 | |||||
Insecticides (Σaverage) | 14,731 ± 1541 | 10,499 ± 1625 | 6059 ± 696 | 19,974 ± 2897 |
EU Legislation | Pesticides | Sado Estuary Annual Average Values (ng/L) | Directive Annual Values (ng/L) | License | log Kow | log Koc | GUS Index | |
---|---|---|---|---|---|---|---|---|
Drinking waters Directive 98/83/EC | Fungicides | |||||||
Azoxystrobin | 393 | 100 | A | 2.5 | 2.8 | 2.6 | ||
Difenoconazole | 1830 | 100 | A | 4.4 | 3.6 | 0.9 | ||
Tebuconazole | 460 | 100 | A | 3.7 | 3.7 | 2.0 | ||
Herbicides | ||||||||
Cyhalofop-butyl | 490 | 100 | A | 6.0 | 3.7 | −0.2 | ||
Metribuzin | 132 | 100 | A | 1.7 | 1.8 | 2.6 | ||
Insecticides | ||||||||
Aldrin | 142 | 100 | B | 6.5 | 4.2 | −0.4 | ||
Azinphos-methyl | 1926 | 100 | NA | 3.0 | 3.0 | 1.0 | ||
Chlorpyriphos | 156 | 100 | A | 4.7 | 3.9 | 0.2 | ||
Chlorfenvinphos | 155 | 100 | NA | 3.8 | 2.8 | 1.9 | ||
Cyfluthrine | 1621 | 100 | A | 5.6 | 4.8 | −1.7 | ||
Cyhalothrin-λ | 380 | 100 | A | 6.8 | 5.2 | −2.1 | ||
Cypermethrin-α | 479 | 100 | A | 6.9 | 4.4 | −2.1 | ||
DDD | 242 | 100 | B | 6.9 | 4.7 | −0.9 | ||
DDE | 101 | 100 | B | 6.9 | 4.9 | −2.0 | ||
DDT | 285 | 100 | B | 6.9 | 5.9 | −4.5 | ||
Deltametrin | 624 | 100 | A | 4.6 | 7.0 | −3.4 | ||
Diazinon | 299 | 100 | NA | 3.7 | 2.8 | 1.1 | ||
Dieldrin | 330 | 100 | B | 3.7 | 4.4 | −0.3 | ||
Dimethoate | 445 | 100 | A | 0.7 | 1.0 | 1.1 | ||
Endosulfan | 547 | 100 | NA | 4.8 | 4.2 | −0.1 | ||
Endosulfan-sulphate | 572 | 100 | NA | 3.7 | 3.7 | 0.5 | ||
Endrin | 534 | 100 | NA | 3.2 | 4.0 | 0.0 | ||
Fenamiphos | 2335 | 100 | A | 3.3 | 2.0 | −0.1 | ||
Methoxychlor | 248 | 100 | NA | 3.8 | 4.9 | −1.9 | ||
Mirex | 410 | 100 | B | 5.3 | 3.8 | 0.6 | ||
Pirimicarb | 111 | 100 | A | 1.7 | 2.6 | 2.7 | ||
Tetrachlorvinphos | 445 | 100 | NA | 3.5 | 3.0 | 0.3 | ||
ΣAldrin,Dieldrin,Heptachlor,Heptachlor epoxide | 1006 | 100 | B; B; B; NA | 5.2 | 4.3 | −0.7 | ||
Concentration (average) of the pesticides above 98/83/EC | 596 | |||||||
EU Legislation | Pesticides | Sado estuary Annual average values (ng/L) | Directive Annual values (ng/L) | License | log Kow | log Koc | GUS index | |
Surface waters Directive 2013/39/EU | Fungicides | |||||||
HCP | 3 | 0.02 | - | 4.0 | 3.6 | 0.4 | ||
PCB | 13 | 7 | NA | 4.8–5.2 | 4.5 | −1.2 | ||
Herbicides | ||||||||
Alachor | 7 | 300 | NA | 3.7 | 2.5 | 0.8 | ||
Atrazine | 9 | 600 | NA | 2.7 | 2.0 | 3.3 | ||
Simazine | 38 | 1000 | NA | 2.3 | 2.1 | 2.0 | ||
Terbutryn | 10 | 65 a–0.65 b | NA | 3.7 | 3.4 | 2.4 | ||
Trifluralin | 3 | 30 | NA | 5.3 | 4.2 | 0.1 | ||
Insecticides | ||||||||
Chlorfenvinphos | 155 | 100 | A | 4.7 | 3.9 | 0.2 | ||
Cypermethrin | 242 | 0.08 a–0.008 b | A | 6.9 | 4.4 | −2.1 | ||
4.4’-DDD | 547 | 25 | B | 6.9 | 4.7 | −0.9 | ||
Dichlorvos | 479 | 0.6 a–0.06 b | NA | 1.9 | 1.7 | 0.7 | ||
Endosulfan | 56 | 5 a–0.5 b | NA | 4.7–4.8 | 4.1–4.3 | −0.1 | ||
Heptachlor | 13 | 2 × 10−4 a–1 ×10−4 b | B | 5.4 | 4.4 | −0.9 | ||
Heptachlor epoxide | 84 | 2 × 10−4 a–1 × 10−4b | NA | 4.4–5.5 | 4.3 | −1.1 | ||
ΣAldrin. Dieldrin. Endrin. Isodrin * | 1006 | 5 a–10 b | B; B; NA; - | 4.5 | 4.2 | −0.2 | ||
The average concentration above 2013/39/EU | 178 | |||||||
a | Inland surface waters | Licence according to the EU Pesticides Database: NA—authorised; A—Authorised; B—Banned | ||||||
b | Other surface waters | GUS index (groundwater ubiquity score; GUS = log10 (half life-days) × [4 − log10 (Koc)]) | ||||||
* | Isodrin was not evaluated in this study |
Pesticides | MEC (mg/L) | Algae 72 h EC50 Growth (mg/L) | Invertebrates 48 h EC50 (mg/L) | Fish 96 h LC50 (mg/L) | PNEC (mg/L) | Individual RQ (MEC/PNEC) | RQ TU Algae (MEC/EC50) | RQ TU Invert. (MEC/EC50) | RQ TU Fish (MEC/EC50) | ||
---|---|---|---|---|---|---|---|---|---|---|---|
FUNGICIDES | Azoxystrobin | 4.5 × 10−3 | 3.6 × 10−1 | 2.3 × 10−1 | 4.7 × 10−1 | 2.3 × 10−3 | 2.0 | 0.0 | 0.0 | 0.0 | |
Difenoconazol | 4.2 × 10−2 | 3.2 × 10−2 | 7.7 × 10−1 | 1.1 × 100 | 3.2 × 10−4 | 130.4 | 1.3 | 0.1 | 0.0 | ||
HCB | 2.2 × 10−5 | 1.0 × 10−2 | 5.0 × 10−1 | 3.0 × 10−2 | 1.0 × 10−4 | 0.2 | 0.0 | 0.0 | 0.0 | ||
PeCB | 1.0 × 10−4 | 1.3 × 10 | - | 2.5 × 10−1 | 2.5 × 10−3 | 0.0 | 0.0 | - | 0.0 | ||
Procymidone | 6.6 × 10−3 | 2.6 × 10 | 1.8 × 100 | 7.2 × 100 | 1.8 × 10−2 | 0.4 | 0.0 | 0.0 | 0.0 | ||
Tebuconazole | 5.4 × 10−3 | 2.0 + | 2.8 × 100 | 4.4 × 100 | 2.0 × 10−2 | 0.3 | 0.0 | 0.0 | 0.0 | ||
HERBICIDES | Alachlor | 5.2 × 10−5 | 9.7 × 10−1 | 1.0 × 10 | 1.8 × 100 | 9.7 × 10−3 | 0.0 | 0.0 | 0.0 | 0.0 | |
Atrazine | 5.8 × 10−5 | 5.9 × 10−2 | 8.5 × 10 | 4.0 × 100 | 5.9 × 10−4 | 0.1 | 0.0 | 0.0 | 0.0 | ||
Atrazine-desethyl | 1.9 × 10−4 | 1.0 × 10−1 | - | - | 1.0 × 10−3 | 0.2 | 0.0 | - | - | ||
Cyanazine | 3.2 × 10−4 | 2.0 × 10−1 | 4.9 × 10 | 1.0 × 101 | 2.0 × 10−3 | 0.2 | 0.0 | 0.0 | 0.0 | ||
Cyhalofop-butyl | 4.9 × 10−3 | 9.6 × 10−1 | 2.7 × 100 | 7.9 × 10−1 | 7.9 × 10−3 | 0.6 | 0.0 | 0.0 | 0.0 | ||
Metolachlor | 2.5 × 10−5 | 5.7 × 101 | 2.4 × 10 | 3.9 × 100 | 3.9 × 10−2 | 0.0 | 0.0 | 0.0 | 0.0 | ||
Metribuzin | 8.7 × 10−4 | 2.0 × 10−2 | 4.9 × 10 | 7.5 × 101 | 2.0 × 10−4 | 4.3 | 0.0 | 0.0 | 0.0 | ||
Pendimethalin | 3.2 × 10−5 | 6.0 × 10−3 | 2.8 × 10−1 | 1.4 × 10−1 | 6.0 × 10−5 | 0.5 | 0.0 | 0.0 | 0.0 | ||
Propazine | 6.9 × 10−4 | 1.8 × 10−1 | 1.8 × 10 | 1.8 × 101 | 1.8 × 10−3 | 0.4 | 0.0 | 0.0 | 0.0 | ||
Propyzamide | 1.9 × 10−4 | 2.8 × 10 | 5.6 × 100 | 4.7 × 100 | 2.8 × 10−2 | 0.0 | 0.0 | 0.0 | 0.0 | ||
Simazine | 2.5 × 10−4 | 4.0 × 10−2 | 1.1 × 100 | 9.0 × 101 | 4.0 × 10−4 | 0.6 | 0.0 | 0.0 | 0.0 | ||
Simetryn | 1.1 × 10−4 | 9.8 × 10−3 | - | 7.0 × 100 | 9.8 × 10−5 | 1.1 | 0.0 | - | 0.0 | ||
Terbuthylazine | 8.4 × 10−4 | 1.2 × 10−2 | 2.1 × 10 | 2.2 × 100 | 1.2 × 10−4 | 7.0 | 0.1 | 0.0 | 0.0 | ||
Terbutryn | 6.3 × 10−5 | 2.4 × 10−3 | 2.7 × 100 | 1.1 × 100 | 2.4 × 10−5 | 2.6 | 0.0 | 0.0 | 0.0 | ||
Trifluralin | 1.9 × 10−5 | 1.2 × 10−2 | 2.5 × 10−1 | 8.8 × 10−2 | 1.2 × 10−4 | 0.2 | 0.0 | 0.0 | 0.0 | ||
INSECTICIDES | Aldrin | 2.5 × 10 −3 | - | 2.8 × 10−2 | 4.6 × 10−3 | 4.6 × 10−5 | 53.7 | - | 0.1 | 0.5 | |
Azinphos-methyl | 2.4 × 10−2 | 7.2 × 100 | 1.1 × 10−3 | 2.0 × 10−2 | 1.1 × 10−5 | 2201.7 | 0.0 | 22.0 | 1.2 | ||
Chlordane-γ | 5.4 × 10−4 | - | 5.9 × 10−1 | 9.0 × 10−2 | 9.0 × 10−4 | 0.6 | - | 0.0 | 0.0 | ||
Chlorpyriphos | 3.3 × 10-3 | 4.8 × 10−1 | 4.0 × 10−5 | 1.3 × 10−3 | 4.0 × 10−7 | 8276.7 | 0.0 | 82.8 | 2.5 | ||
Chlorfenvinphos | 3.0 × 10−3 | 1.4 × 100 | 2.5 × 10−4 | 1.1 × 100 | 2.5 × 10−6 | 1200.3 | 0.0 | 12.0 | 0.0 | ||
Cyfluthrin | 3.1 × 10−2 | 1.0 × 10 | 1.6 × 10−4 | 4.7 × 10−4 | 1.6 × 10−6 | 19,631.9 | 0.0 | 196.3 | 66.8 | ||
Cyhalothrin- γ | 4.9 × 10−3 | - | 3.8 × 10−1 | 4.6 × 10−4 | 4.6 × 10−6 | 1064.6 | - | 0.0 | 10.6 | ||
Cypermethrin-α | 6.0 × 10−3 | 1.0 × 10−1 | 3.0 × 10−4 | 2.8 × 10−3 | 3.0 × 10−6 | 1990.2 | 0.1 | 19.9 | 2.1 | ||
ΣDDD,DDE,DDT | 1.3 × 10−2 | - | 5.0 × 10−3 | 7.0 × 100 | 5.0 × 10−5 | 265.3 | - | 2.7 | 0.0 | ||
Deltametrin | 9.1 × 10−3 | 9.1 × 100 | 5.6 × 10−4 | 2.6 × 10−4 | 2.6 × 10−6 | 3511.8 | 0.0 | 16.3 | 35.1 | ||
Diazinon | 2.6 × 10−3 | 6.4 × 100 | 1.0 × 10−3 | 3.1 × 100 | 1.0 × 10−5 | 260.2 | 0.0 | 2.6 | 0.0 | ||
Dichlorvos | 4.5 × 10−4 | 5.3 × 10 | 1.9 × 10−4 | 5.5 × 10−1 | 1.9 × 10−6 | 236.3 | 0.0 | 2.4 | 0.0 | ||
Dieldrin | 6.6 × 10−3 | 1.0 × 10−1 | 2.5 × 10−1 | 1.2 × 10−3 | 1.2 × 10−5 | 549.7 | 0.1 | 0.0 | 5.5 | ||
Dimethoate | 3.0 × 10−3 | 9.0 × 10 | 2.0 × 100 | 3.0 × 10 | 2.0 × 10−2 | 0.1 | 0.0 | 0.0 | 0.0 | ||
Endosulfan (α + β) | 9.1 × 10−3 | 2.2 × 100 | 4.4 × 10−1 | 2.0 × 10−3 | 2.0 × 10−5 | 456.5 | 0.0 | 0.0 | 4.6 | ||
Endosulfan sulfate | 5.9 × 10−3 | - | - | - | - | - | - | - | - | ||
Endrin | 1.1 × 10−2 | - | 4.20 × 10−3 | 7.3 × 10−4 | 7.3 × 10−6 | 1250.8 | - | 2.2 | 12.5 | ||
Fenamiphos | 4.3 × 10−2 | 3.8 × 100 | 1.90 × 10−3 | 9.3 × 10−3 | 1.9 × 10−5 | 2272.0 | 0.0 | 22.7 | 4.6 | ||
Fenitrothion | 9.1 × 10−5 | 1.3 × 100 | 8.60 × 10−3 | 1.3 × 100 | 8.6 × 10−5 | 1.1 | 0.0 | 0.0 | 0.0 | ||
Fonofos | 5.3 × 10−4 | 1.5 × 100 | 2.30 × 10−3 | 2.8 × 10−2 | 2.3 × 10−5 | 23.0 | 0.0 | 0.2 | 0.0 | ||
Heptachlor | 2.7 × 10−4 | 2.7 × 10−2 | 4.20 × 10−2 | 7.0 × 10−3 | 7.0 × 10−5 | 3.9 | 0.0 | 0.0 | 0.0 | ||
Heptachlor epoxide | 9.2 × 10−4 | 2.0 × 102 | 2.40 × 10−1 | 2.0 × 10−2 | 2.0 × 10−4 | 4.6 | 0.0 | 0.0 | 0.0 | ||
HCCP | 8.0 × 10−7 | - | 5.20 × 10−2 | 2.4 × 100 | 5.2 × 10−4 | 0.0 | - | 0.0 | 0.0 | ||
Lindane | 2.1 × 10−4 | 2.5 × 100 | 1.60 × 100 | 2.9 × 10−3 | 2.9 × 10−5 | 7.4 | 0.0 | 0.0 | 0.1 | ||
Malathion | 1.2 × 10−4 | 1.3 × 10 | 7.0 × 10−4 | 1.8 × 10−2 | 7.0 × 10−6 | 17.4 | 0.0 | 0.2 | 0.0 | ||
Methoxychlor | 2.6 × 10−3 | 6.0 × 10−1 | 7.8 × 10−4 | 5.2 × 10−2 | 7.8 × 10−6 | 329.8 | 0.0 | 3.3 | 0.0 | ||
Mirex | 5.8 × 10−3 | 1.0 × 10−1 | 1.0 × 10−1 | 1.0 × 102 | 1.0 × 10−3 | 5.8 | 0.1 | 0.1 | 0.0 | ||
∑Parathion-methyl. ethyl | 1.5 × 10−4 | 3.0 × 100 | 7.3 × 10−3 | 2.7 × 100 | 7.3 × 10−5 | 2.0 | 0.0 | 0.0 | 0.0 | ||
Phosmet | 4.4 × 10−4 | 7.0 × 10−2 | 2.0 × 10−3 | 2.3 × 10−1 | 2.0 × 10−5 | 21.9 | 0.0 | 0.2 | 0.0 | ||
Pirimicarb | 7.7 × 10−4 | 1.4 × 102 | 1.7 × 10−2 | 1.0 × 102 | 1.7 × 10−4 | 4.5 | 0.0 | 0.0 | 0.0 | ||
Tetrachlorvinphos | 5.3 × 10−3 | - | 2.0 × 10−3 | 4.3 × 10−1 | 2.0 × 10−5 | 262.9 | - | 2.6 | 0.0 | ||
∑RQMEC/PNEC | 44,058 | ||||||||||
First-tier (CA-based) | 1.7 | 388.8 | 146.6 | ||||||||
RQSTU | 38,875 | ||||||||||
Second-tier (IA-based) | maxRQSTU/maxTU | 2.0 |
Season | Sites | T (°C) | pH | DO (mg/L) | Salinity (PSU) | Nitrites (mg/L) | Nitrates (mg/L) | Ammonium (mg/L) | Phosphates (mg/L) |
---|---|---|---|---|---|---|---|---|---|
Spring (n = 5) | A–E | 16.9 ± 1.1 | 8.0 ± 0.3 | 7.8 ± 2.0 | 31.1 ± 3.7 | 0.02 ± 0.0 | 0.2 ± 0.1 | 0.6 ± 0.5 | 0.6 ± 1.9 |
Summer (n = 10) | 20.4 ± 1.9 | 8.1 ± 0.2 | 6.6 ± 2.4 | 34.8 ± 1.3 | 0.04 ± 0.1 | 0.2 ± 0.2 | 0.6 ± 0.6 | 1.2 ± 1.4 | |
Autumn (n = 10) | 14.1 ± 2.3 | 8.4 ± 0.2 | 8.2 ± 1.0 | 31.0 ± 5.4 | 0.02 ± 0.0 | 0.4 ± 0.2 | 1.1 ± 1.5 | 0.7 ± 1.0 | |
Winter (n = 5) | 12.7 ± 2.6 | 8.2 ± 0.1 | 9.3 ± 0.5 | 28.8 ± 5.6 | 0.03 ± 0.0 | 0.4 ± 0.2 | 0.5 ± 0.4 | 0.01 ± 0.0 | |
Spring (n = 4) | F–I | 17.6 ± 0.4 | 7.7 ± 0.3 | 6.0 ± 1.8 | 16.9 ± 13.8 | 0.03 ± 0.0 | 1.0 ± 0.5 | 0.8 ± 0.6 | 0.5 ± 0.3 |
Summer (n = 8) | 22.3 ± 2.1 | 7.9 ± 0.3 | 5.4 ± 1.9 | 12.8 ± 14.7 | 0.07 ± 0.1 | 1.3 ± 2.6 | 0.7 ± 0.9 | 3.0 ± 1.6 | |
Autumn (n = 8) | 12.6 ± 3.6 | 8.1 ± 0.3 | 7.6 ± 1.4 | 10.0 ± 13.1 | 0.06 ± 0.0 | 1.0 ± 0.7 | 0.4 ± 0.3 | 0.8 ± 0.5 | |
Winter (n = 4) | 11.2 ± 0.5 | 7.9 ± 0.4 | 6.5 ± 4.8 | 12.8 ± 13.5 | 0.07 ± 0.0 | 0.2 ± 0.4 | 0.4 ± 0.2 | 0.3 ± 0.6 |
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Rocha, M.J.; Rocha, E. Chemical Survey and Risk Assessment of 56 Pesticides in the Sado River Estuary (Iberian Peninsula, Portugal). Toxics 2023, 11, 457. https://doi.org/10.3390/toxics11050457
Rocha MJ, Rocha E. Chemical Survey and Risk Assessment of 56 Pesticides in the Sado River Estuary (Iberian Peninsula, Portugal). Toxics. 2023; 11(5):457. https://doi.org/10.3390/toxics11050457
Chicago/Turabian StyleRocha, Maria João, and Eduardo Rocha. 2023. "Chemical Survey and Risk Assessment of 56 Pesticides in the Sado River Estuary (Iberian Peninsula, Portugal)" Toxics 11, no. 5: 457. https://doi.org/10.3390/toxics11050457