Degradation of pharmaceuticals and metabolite in synthetic human urine by UV, UV/H2O2, and UV/PDS

Ruochun Zhang, Peizhe Sun, Treavor Boyer, Lin Zhao, Ching Hua Huang

Research output: Contribution to journalArticle

158 Citations (Scopus)

Abstract

To minimize environmental pharmaceutical micropollutants, treatment of human urine could be an efficient approach due to the high pharmaceutical concentration and toxic potential excreted in urine. This study investigated the degradation kinetics and mechanisms of sulfamethoxazole (SMX), trimethoprim (TMP) and N4-acetyl-sulfamethoxazole (acetyl-SMX) in synthetic fresh and hydrolyzed human urines by low-pressure UV, and UV combined with H2O2 and peroxydisulfate (PDS). The objective was to compare the two advanced oxidation processes (AOPs) and assess the impact of urine matrices. All three compounds reacted quickly in the AOPs, exhibiting rate constants of (6.09-8.53) × 109 M-1·s-1 with hydroxyl radical, and (2.35-16.1) × 109 M-1·s-1 with sulfate radical. In fresh urine matrix, the pharmaceuticals' indirect photolysis was significantly suppressed by the scavenging effect of urine citrate and urea. In hydrolyzed urine matrix, the indirect photolysis was strongly affected by inorganic urine constituents. Chloride had no apparent impact on UV/H2O2, but significantly raised the hydroxyl radical concentration in UV/PDS. Carbonate species reacted with hydroxyl or sulfate radical to generate carbonate radical, which degraded SMX and TMP, primarily due to the presence of aromatic amino group(s) (k = 2.68 × 108 and 3.45 × 107 M-1·s-1) but reacted slowly with acetyl-SMX. Ammonia reacted with hydroxyl or sulfate radical to generate reactive nitrogen species that could react appreciably only with SMX. Kinetic simulation of radical concentrations, along with products analysis, helped elucidate the major reactive species in the pharmaceuticals' degradation. Overall, the AOPs' performance was higher in the hydrolyzed urine than fresh urine matrix with UV/PDS better than UV/H2O2, and varied significantly depending on pharmaceutical's structure.

Original languageEnglish (US)
Pages (from-to)3056-3066
Number of pages11
JournalEnvironmental Science and Technology
Volume49
Issue number5
DOIs
StatePublished - Mar 3 2015
Externally publishedYes

Fingerprint

Metabolites
urine
metabolite
drug
Sulfamethoxazole
Hydroxyl Radical
Urine
Degradation
degradation
Pharmaceutical Preparations
Carbonates
Sulfamethoxazole Drug Combination Trimethoprim
Photolysis
Oxidation
Reactive Nitrogen Species
Kinetics
matrix
Poisons
Scavenging
hydroxyl radical

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry
  • Medicine(all)

Cite this

Degradation of pharmaceuticals and metabolite in synthetic human urine by UV, UV/H2O2, and UV/PDS. / Zhang, Ruochun; Sun, Peizhe; Boyer, Treavor; Zhao, Lin; Huang, Ching Hua.

In: Environmental Science and Technology, Vol. 49, No. 5, 03.03.2015, p. 3056-3066.

Research output: Contribution to journalArticle

Zhang, Ruochun ; Sun, Peizhe ; Boyer, Treavor ; Zhao, Lin ; Huang, Ching Hua. / Degradation of pharmaceuticals and metabolite in synthetic human urine by UV, UV/H2O2, and UV/PDS. In: Environmental Science and Technology. 2015 ; Vol. 49, No. 5. pp. 3056-3066.
@article{7694ce5922794a34b527fe7d82907c81,
title = "Degradation of pharmaceuticals and metabolite in synthetic human urine by UV, UV/H2O2, and UV/PDS",
abstract = "To minimize environmental pharmaceutical micropollutants, treatment of human urine could be an efficient approach due to the high pharmaceutical concentration and toxic potential excreted in urine. This study investigated the degradation kinetics and mechanisms of sulfamethoxazole (SMX), trimethoprim (TMP) and N4-acetyl-sulfamethoxazole (acetyl-SMX) in synthetic fresh and hydrolyzed human urines by low-pressure UV, and UV combined with H2O2 and peroxydisulfate (PDS). The objective was to compare the two advanced oxidation processes (AOPs) and assess the impact of urine matrices. All three compounds reacted quickly in the AOPs, exhibiting rate constants of (6.09-8.53) × 109 M-1·s-1 with hydroxyl radical, and (2.35-16.1) × 109 M-1·s-1 with sulfate radical. In fresh urine matrix, the pharmaceuticals' indirect photolysis was significantly suppressed by the scavenging effect of urine citrate and urea. In hydrolyzed urine matrix, the indirect photolysis was strongly affected by inorganic urine constituents. Chloride had no apparent impact on UV/H2O2, but significantly raised the hydroxyl radical concentration in UV/PDS. Carbonate species reacted with hydroxyl or sulfate radical to generate carbonate radical, which degraded SMX and TMP, primarily due to the presence of aromatic amino group(s) (k = 2.68 × 108 and 3.45 × 107 M-1·s-1) but reacted slowly with acetyl-SMX. Ammonia reacted with hydroxyl or sulfate radical to generate reactive nitrogen species that could react appreciably only with SMX. Kinetic simulation of radical concentrations, along with products analysis, helped elucidate the major reactive species in the pharmaceuticals' degradation. Overall, the AOPs' performance was higher in the hydrolyzed urine than fresh urine matrix with UV/PDS better than UV/H2O2, and varied significantly depending on pharmaceutical's structure.",
author = "Ruochun Zhang and Peizhe Sun and Treavor Boyer and Lin Zhao and Huang, {Ching Hua}",
year = "2015",
month = "3",
day = "3",
doi = "10.1021/es504799n",
language = "English (US)",
volume = "49",
pages = "3056--3066",
journal = "Environmental Science & Technology",
issn = "0013-936X",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Degradation of pharmaceuticals and metabolite in synthetic human urine by UV, UV/H2O2, and UV/PDS

AU - Zhang, Ruochun

AU - Sun, Peizhe

AU - Boyer, Treavor

AU - Zhao, Lin

AU - Huang, Ching Hua

PY - 2015/3/3

Y1 - 2015/3/3

N2 - To minimize environmental pharmaceutical micropollutants, treatment of human urine could be an efficient approach due to the high pharmaceutical concentration and toxic potential excreted in urine. This study investigated the degradation kinetics and mechanisms of sulfamethoxazole (SMX), trimethoprim (TMP) and N4-acetyl-sulfamethoxazole (acetyl-SMX) in synthetic fresh and hydrolyzed human urines by low-pressure UV, and UV combined with H2O2 and peroxydisulfate (PDS). The objective was to compare the two advanced oxidation processes (AOPs) and assess the impact of urine matrices. All three compounds reacted quickly in the AOPs, exhibiting rate constants of (6.09-8.53) × 109 M-1·s-1 with hydroxyl radical, and (2.35-16.1) × 109 M-1·s-1 with sulfate radical. In fresh urine matrix, the pharmaceuticals' indirect photolysis was significantly suppressed by the scavenging effect of urine citrate and urea. In hydrolyzed urine matrix, the indirect photolysis was strongly affected by inorganic urine constituents. Chloride had no apparent impact on UV/H2O2, but significantly raised the hydroxyl radical concentration in UV/PDS. Carbonate species reacted with hydroxyl or sulfate radical to generate carbonate radical, which degraded SMX and TMP, primarily due to the presence of aromatic amino group(s) (k = 2.68 × 108 and 3.45 × 107 M-1·s-1) but reacted slowly with acetyl-SMX. Ammonia reacted with hydroxyl or sulfate radical to generate reactive nitrogen species that could react appreciably only with SMX. Kinetic simulation of radical concentrations, along with products analysis, helped elucidate the major reactive species in the pharmaceuticals' degradation. Overall, the AOPs' performance was higher in the hydrolyzed urine than fresh urine matrix with UV/PDS better than UV/H2O2, and varied significantly depending on pharmaceutical's structure.

AB - To minimize environmental pharmaceutical micropollutants, treatment of human urine could be an efficient approach due to the high pharmaceutical concentration and toxic potential excreted in urine. This study investigated the degradation kinetics and mechanisms of sulfamethoxazole (SMX), trimethoprim (TMP) and N4-acetyl-sulfamethoxazole (acetyl-SMX) in synthetic fresh and hydrolyzed human urines by low-pressure UV, and UV combined with H2O2 and peroxydisulfate (PDS). The objective was to compare the two advanced oxidation processes (AOPs) and assess the impact of urine matrices. All three compounds reacted quickly in the AOPs, exhibiting rate constants of (6.09-8.53) × 109 M-1·s-1 with hydroxyl radical, and (2.35-16.1) × 109 M-1·s-1 with sulfate radical. In fresh urine matrix, the pharmaceuticals' indirect photolysis was significantly suppressed by the scavenging effect of urine citrate and urea. In hydrolyzed urine matrix, the indirect photolysis was strongly affected by inorganic urine constituents. Chloride had no apparent impact on UV/H2O2, but significantly raised the hydroxyl radical concentration in UV/PDS. Carbonate species reacted with hydroxyl or sulfate radical to generate carbonate radical, which degraded SMX and TMP, primarily due to the presence of aromatic amino group(s) (k = 2.68 × 108 and 3.45 × 107 M-1·s-1) but reacted slowly with acetyl-SMX. Ammonia reacted with hydroxyl or sulfate radical to generate reactive nitrogen species that could react appreciably only with SMX. Kinetic simulation of radical concentrations, along with products analysis, helped elucidate the major reactive species in the pharmaceuticals' degradation. Overall, the AOPs' performance was higher in the hydrolyzed urine than fresh urine matrix with UV/PDS better than UV/H2O2, and varied significantly depending on pharmaceutical's structure.

UR - http://www.scopus.com/inward/record.url?scp=84924023293&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84924023293&partnerID=8YFLogxK

U2 - 10.1021/es504799n

DO - 10.1021/es504799n

M3 - Article

C2 - 25625668

AN - SCOPUS:84924023293

VL - 49

SP - 3056

EP - 3066

JO - Environmental Science & Technology

JF - Environmental Science & Technology

SN - 0013-936X

IS - 5

ER -