Distribution and Ecological Risk Assessment of Typical Antibiotics In
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Electronic Supplementary Material (ESI) for Environmental Science: Processes & Impacts. This journal is © The Royal Society of Chemistry 2021 Distribution and ecological risk assessment of typical antibiotics in surface waters of seven major rivers, China Zhizhen Yin The Key Laboratory of pollutant Chemistry and Environmental Treatment, School of Chemistry and environment Sciences, Yili Normal University, Yining 835000, China. E-mail: [email protected] Contents of supporting information Table S1 Summary of the extraction and separation methods for antibiotics in surface waters of seven major rivers in china reported in the literature between 2010 and 2020 Table S2 Summary of the aquatic toxicity data and minimum PNEC values of target antibiotics Table S3 Sampling sites of studies on target antibiotics in surface waters of seven major rivers in China Table S1 Summary of the extraction and separation methods for antibiotics in surface waters of seven major rivers in china reported in the literature between 2010 and 2020 Pretreatment method Extraction Separation Detection Refere nce Water samples (1 L) were filtered through 0.22 NA BEH C18 column (50 mm × 2.1 mm, 1.7 µm) LOD: 0.071～0.432 ng/L; 1 µm micropore membranes. The mobile phase contained 0.01% formic acid in pure LOQ: 0.21～1.369 ng/L; water (A) and 100% acetonitrile (B). Recovery: 81.12～115.69% Water samples were filtered through 0.45 μm Oasis HLB cartridges (500 mg, 6mL) BEH C18 column (100 mm × 2.1 mm, 1.7 μm) LOQ: 0.05～5 ng/L; 2 glass fiber filters and then acidified to pH 3 by Pretreatment: methanol (6 mL) and ultrapure water (6mL). Rinse: Recovery: 84.5～107.3%; adding HCl. 0.2 g/L Na2EDTA was added into 6 mL ultrapure water. Elution: 6mL ultrapure water and 12 mL RSD: <5% water samples. methanol. Water samples were adjusted to pH 3 using Oasis HLB cartridges (200mg, 6 m) BEH C18 column (100 mm × 2.1 mm, 1.7 μm) . LOD: 0.02～5.03 ng/L; 3 H2SO4, added with 5% methanol. Pretreatment: methanol (10 mL) and Milli-Q water (10mL). Rinse: The mobile phase contained 0.1% formic acid in Milli- Recovery: 40～140% 10 mL Milli-Q water. Elution: 12 mL methanol. Q water (A) and acetonitrile (B). Water samples were filtered through 0.7 μm Elution: 10 mL methanol. HSS T3 column (100 mm × 2.1 mm, 1.8 μm) LOD: 0.01～1.07 ng/L; 4 glass fiber filters and acidified to pH 4 with The mobile phase contained 0.1% formic acid in LOQ: 0.03～1.71 ng/； formic acid, followed by the addition of 0.2 g/L ultrapure water (A) and acetonitrile with 0.1% formic Recovery: 63.0～126.8% ; Na2EDTA. acid (B). RSD: < 5.5% Water samples were filtered by glass fiber Strata-X cartridges (200 mg, 6 mL) Supelco Discovery HS C18 column (150 mm × 4.6 mm, LOQ: 0.15～9.1 ng/L; 5 filter, and then pH was adjusted to 5. Pretreatment: deionized water (6 mL) and methanol (6 mL). 3 µm) Recovery: 77～159% Rinse: 6 mL deionized water. Elution: 3 mL methanol. The mobile phase contained 0.1% formic acid in ultrapure water (A) and acetonitrile (B) Water samples were acidified to pH 4.0 with Oasis HLB cartridges (200 mg, 6 mL) HSS T3 column (100 mm × 2.1 mm, 1.8 μm ) LOD: 0.01～1.18 ng/L; 6 citrate buffer, followed by the addition of 0.2 Pretreatment: methanol (6mL) and ultrapure water (10mL). Ultrapure water containing 0.1% formic acid (A) and LOQ: 0.03～1.68 ng/L; g/L Na2EDTA. Elution: 10 mL methanol. acetonitrile containing 0.1% formic acid (B) was used Recovery: 62.1～129.4% as the mobile phase. Water sample was filtered through 0.45 μm Oasis HLB cartridges Poroshell 120 EC-C18 (2.1 mm × 75 mm, 2.7 μm) LOD: 0.1～1.6 ng/L; 7 fiber filters and acidified to pH 3 with H3PO4, Pretreatment: methanol (6 mL) and ultrapure water (3 mL) and The mobile phase contained acetonitrile (A) and 0.2% Recovery: 74.3～95.8%; followed by the addition of 100 g/L Na2EDTA. sodium dihydrogen phosphate solution (6 mL). Rinse: 6 mL formic acid in ultrapure water (B). RSD: 4.7～9.5% ultrapure. Elution: 3 mL methanol and 6 mL methanol with 2% ammonia Water sample (1L) was filtered through 0.45 Pretreatment: methanol (6 mL) and ultrapure water (3 mL) and ZORBAX Eclipse Plus C18 (150 mm × 2. 1 mm，3.5 LOD: 0.03～15 ng/L; 8 μm fiber filters, and then 5 mL of 100g/L sodium dihydrogen phosphate solution (6 mL). Rinse: 6 mL μm) Recovery: 41.3～112. 6%; Na2EDTA was added and the pH was adjusted ultrapure water. Elution: 6 mL methanol with 2% ammonia. The mobile phase contained 0.2% formic acid in RSD: 0.2～12. 7% to 4 with 50% H3PO4. ultrapure water (A) and acetonitrile (B). Water samples were filtered through 0.22 μm Poly-Sery HLB cartridges C18 (2.1 mm× 50 mm, 1.8 μm) Recovery: 69～125% 9 fiber filters and then acidified to pH 3 by Pretreatment: methanol (10 mL) and ultrapure water (10 mL). The mobile phase contained 0.2% formic acid (A) and adding HCl, followed by the addition of 0.5g Rinse: 5 mL methanol with 5% ammonia and 10 mL ultrapure acetonitrile (B). Na2EDTA. water. Elution: 10 mL methanol. Water sample (1L) was filtered through 0.45 Oasis HLB cartridge NA LOQ: 1～20 ng/L; 10 μm glass fiber filters and acidified to pH 3. Rinse: ultrapure water. Elution: methanol. Recovery: 61～86% Water samples (1L) were filtered through 0.45 HLB cartridges C18 (4.6 mm × 150 mm, 3.5 μm) LOQ: 0.1～1.4 ng/L; 11 μm glass fiber filters and acidified to pH 3 by Pretreatment: methanol (6 mL) and ultrapure water (6 mL). The mobile phase contained 0.1% formic acid in Recovery: 73～92%; adding H2SO4, followed by the addition of 10 ultrapure water (A) and acetonitrile with 0.1% formic RSD: <20% mL of 5% Na2EDTA. acid (B). Water samples were filtered through 0.7 μm Oasis HLB (200 mg，6mL) Agilent ZORBAX Eclipse Plus C18 (100 mm × 2.1 mm, Recovery: 31.4～158.8%; 12 fiber filters and then 0.5g Na2EDTA was added. Pretreatment: methanol (10 mL) and ultrapure water (10 mL). 1.8 μm) RSD: <20% Samples were acidified to pH 3 by adding Rinse: 10 mL ultrapure. Elution: 10 mL methanol. The mobile phase contained 0.2% formic acid and 2 4mol/L HCl. mmol/L ammonium acetate (A) and acetonitrile (B). Water samples (1L) were filtered through 0.7 HLB (1000 mg) Agilent ZORBAX Eclipse Plus C18 (100 mm × 2. 1 LOD: 0.4～10 ng/L; 13 μm fiber filters and then acidified to pH 3 by Elution: 10 mL methanol. mm， 1. 8 μm) Recovery: 61.4～131.5% adding H2SO4, followed by the addition of 5% The mobile phase contained 0.1% formic acid and 5 RSD: <20% methanol. mmol/L ammonium acetate (A) and acetonitrile (B). The pH values of the water samples were Oasis HLB (500 mg, 6 mL) XDB-C18 column (2.1 mm × 50 mm, 1.8 µm) LOQ: 0.077～5.3 ng/L; 14 adjusted to 3 by adding H2SO4 and then Pretreatment: methanol (10 mL) and ultra-pure water (10 mL). The mobile phase contained acetonitrile (A) and 5mM Recovery: 66～158%; filtered through 0.7 μm fiber filters, followed Rinse: 10 mL Milli-Q water. Elution: 12 mL methanol. oxalic acid (B). RSD: 1～10% by the addition of 1 g Na2EDTA. Water samples were filtered through 0.7 µm HLB (500 mg, 6 mL) Agilent ZORBAX C18 (2.1 mm × 150 mm, 5 µm ) LOQ: 0.22～9.96ng/L; 15 fiber filters by the addition of 10 mL of 5% Pretreatment: methanol (6 mL) and Milli-Q water (6 mL). Rinse: The mobile phase contained acetonitrile (A) and 0.2% Recovery: 55.3～108%; Na2EDTA. The pH value was adjusted to 3 10 mL Milli-Q water. Elution: 6 mL methanol. formic acid (B). RSD: <14% using formic acid. Water samples were filtered through 0.7 μm HLB (500 mg, 6 mL) ZORBAX Eclipse Plus C18 (2.1 mm × 50 mm, 1.8 μm) LOD: 0.004～0.6 ng/L; 16 glass fiber filters and then acidified pH to 3 by Pretreatment: methanol (10 mL) Milli-Q water (10 mL). Rinse: and ZORBAX SB C18 (2.1 mm × 100 mm, 1.8 μm) Recovery: 70～120% adding H2SO4, followed by the addition of 0.5 g Milli-Q water (10 mL). Elution: 10 mL methanol. The mobile phase contained water (A) and Na2EDTA. acetonitrile (B). NA HLB (200mg, 6mL) XTerra MS C18 (2.1 mm × 100 mm, 3.5 mm) MDL: 0.01～0.25 ng /L; 17 Pretreatment: methanol (5 mL) and ultrapure water (2 mL). Recovery: 57.4～138% Rinse: 12 mL ultrapure water. Elution: 6 mL methanol. Water samples were filtered through 0.45 µm Oasis HLB (500 mg, 6mL) Intersil ODS-3 (2.1 mm × 250 mm, 5 μm) Recovery: 58～91%; 18 fiber filters, and adjusted to pH 5 with citrate Pretreatment: methanol (5 mL) and pure water (5 mL). Rinse: 5 The mobile phase contained acetonitrile (A) and RSD: 0.5～2.5% buffer. 0.2 g Na2EDTA was added into samples.