Development Method for Extracting and Analyzing Antibiotic and Hormone Residues from Treated Wastewater Sludge and Composted Biosolids

Extraction and analysis methods have been developed for the detection of the following four antibacterial agents and two natural estrogens in treated municipal wastewater sludge and commercial compost: sulfamethoxazole (SMX), sulfadimethoxine (SDM), tetracycline (TET), oxytetracycline (OXY), estrone (E1), and 17β-estradiol (E2). The antibiotics and estrogens were extracted from secondary sludge and mixed compost using ultrasonic solvent extraction. Citric acid (pH 4.7) and methanol were used as extraction buffer, followed by tandem-solid-phase extraction cleanup, strong anion exchange + hydrophilic–lipophilic balance for antibiotics and CarboPrep/NAX for estrogens. For quantification, two different methods were employed, using HPLC–MS/MS, with an electrospray ionization source for antibiotics and an atmospheric-pressure chemical ionization source for estrogens. Recoveries were 11–31% for the sulfonamides (SMX and SDM) and tetracyclines (TET and OXY) and 30–59% for the estrogens (E1 and E2) over the entire method. Limits of detection for the extraction method were in the nanogram per gram range for dry weight sludge and compost samples. Neither of the two sulfonamide antibiotics was detected in secondary sludge or mixed compost samples. Estrogens were found in compost in amounts of 160 ± 65 ng/g (E1) and 21 ± 3 ng/g (E2), but not in sludge. The tetracyclines, as well as what is believed to be the 4-epimer of OXY, were found in both sludge and compost in amounts of 1.57 ± 0.67 and 2.95 ± 0.42 μg/g (TET), 0.56 ± 0.12 and 6.51 ± 0.52 μg/g (OXY), and 7.60 ± 1.68 and 1.35 ± 0.24 μg/g (4-epi-OXY), respectively. These results indicate that sorption-prone compounds are not removed during the wastewater treatment process and can persist through sludge digestion and that the composting process does not sufficiently eliminate these particular contaminants. Thus, biosolids (even composted) are an additional source of drug residues leaching into the environment, and it must be considered while using biosolids as fertilizer.