Rainfall Influences Occurrence of Pharmaceutical and Personal Care Products in Landfill Leachates: Evidence from Seasonal Variations and Extreme Rainfall Episodes.

Unused or expired pharmaceutical and personal care products (PPCPs) are usually discharged into municipal solid wastes, then travel to landfills, and eventually percolate into leachates. However, knowledge of their occurrence and temporal dynamics in leachates is limited, making landfill leachate an underappreciated emission source of PPCPs. Furthermore, the differences in PPCP variations in landfill leachates emphasize the necessity for identifying the influencing factors and elucidating the mechanisms for PPCP fluctuations. In this study, successive monthly monitoring of PPCPs in leachates throughout an entire year was performed to determine their seasonal variations and identify their influencing factors. Furthermore, five pairs of additional sampling campaigns were conducted before and after rainfall events during wet seasons to elucidate the influencing mechanisms. The results showed that there was a distinct seasonal variation in PPCPs in landfill leachates-elevated levels during the wet period (from April to September, with a mean concentration of 17.0 µg/L for total monitored PPCPs)-when compared to other months (mean concentration of 3.8 µg/L). Rainfall played a considerable role in mediating PPCP concentrations in leachates. The PPCP responses to five rainfall episodes further verified the influence of rainfall and demonstrated that the tendency to PPCP concentration increase was related to rainfall precipitation. Torrential rain events (i.e., 24 h cumulative precipitation of 50-99.9 mm) led to the most significant increases in PPCP concentrations in landfill leachates. In addition, the hydrophilicity of PPCPs contributed to the different fluctuations during the 1 year investigation and different responses to rainfall. To the best of our knowledge, this study provides the first direct evidence supporting the influence of rainfall on PPCPs in landfill leachates, which can help better understand the occurrence and behavior of emerging contaminants in this underappreciated emission source.

Non-antibiotics matter: Evidence from a one-year investigation of livestock wastewater from six farms in East China.

Livestock wastewater is an important source of pharmaceuticals in aquatic environments; however, most related studies only focused on antibiotics. This study investigated 18 pharmaceutical active compounds (PhACs), including 12 antibiotics and 6 non-antibiotics, in livestock wastewater during a one-year survey of six livestock farms in East China. The results showed that four non-antibiotic PhACs-caffeine, N,N-diethyl-m-toluamide, gemfibrozil, and diclofenac-exhibited high detection frequencies (80% to 97%), high concentrations (median 0.43 to 3.79 µg/L), poor removal efficiencies (3% to 53%), and high environmental risks. A ranking system was developed to prioritize PhACs based on their occurrence, removal, and environmental risks in livestock wastewater; diclofenac, N,N-diethyl-m-toluamide, sulfamethazine, sulfadiazine, and gemfibrozil, were identified as the top five priority PhACs that should be considered first. Finally, a preliminary source apportionment protocol using four priority PhACs was proposed to trace the emission originating from treated and untreated livestock wastewater and to indicate the major contributor (cattle or swine farms) in the region. To the best of our knowledge, this is the first long-term investigation on the pollution characteristics of non-antibiotics in livestock wastewater in China, and our findings highlight the importance of considering non-antibiotics and the prioritized PhACs for the pollution control of PhACs in livestock wastewater.

Identification of indicator PPCPs in landfill leachates and livestock wastewaters using multi-residue analysis of 70 PPCPs: Analytical method development and application in Yangtze River Delta, China.

The source apportionment of pharmaceuticals and personal care products (PPCPs) in the water environment based on indicators (i-PPCPs) requires a comprehensive characterization of various emission sources using reliable analytical methods for a wide spectrum of PPCPs. In this study, a robust and sensitive method based on solid phase extraction (SPE) and ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) for analyzing 70 PPCPs belonging to 17 therapeutic classes in landfill leachates and livestock wastewaters was developed. The SPE cartridges, sample pH, elution solvents and chelating agent additions were optimized, and acceptable recoveries (60- 130% for 67 target compounds), low method quantification limits (landfill leachate: 3- 1309 ng/L; livestock wastewater: 3- 686 ng/L) and high precisions (repeatability: 0- 20% for over 99% injections; reproducibility: 0- 20% for over 90% injections) were obtained. Using the optimized analytical method to characterize PPCPs in the typical landfill leachate and livestock wastewater in Yangtze River Delta, China, we found anthelmintics, which were first reported in landfill leachates globally, exhibited the highest concentration (albendazole, maximum concentration of 61.6 µg/L), and therefore proposed albendazole as one of the promising i-PPCP candidates in landfill leachates. In livestock wastewaters, antibiotics lincomycin was the most abundant PPCP (maximum concentration: 735 µg/L) and identified as an i-PPCP candidate for livestock-originated contamination. In addition, 15 non-antibiotic PPCPs were first investigated in the livestock wastewater in China and some non-steroidal anti-inflammatory drugs, acetaminophen, diclofenac and naproxen, were detected at similar concentration level (1.16- 91.1 µg/L) to antibiotics, highlighting the necessity to include representative non-antibiotic PPCPs in the studies of emerging contaminants in livestock wastewaters. The developed method provides a tool to comprehensively investigate PPCPs in high-strength wastewater, and the preliminary findings in the characterization of typical landfill leachates and livestock wastewaters are helpful to select i-PPCPs for the source apportionment of PPCPs in Yangtze River Delta, China.