A novel approach to identify priority areas for optimal nutrient management in mixed land-use watersheds through nutrient budget assessment.

Excessive nutrient supply in agricultural regions has led to various environmental issues, thereby requiring concentrated management owing to its persistent upward trend. Nutrient budgets (NBs), a vital agricultural environmental indicator, are employed for nutrient management in agricultural areas, using data surveyed by administrative agencies. However, the spatial extent of nutrient data for nutrient budgeting is limited by administrative boundaries according to the surveying organization, posing challenges in interpreting spatial patterns at the watershed level. In this study, a novel approach was developed to identify priority nutrient management areas by applying hot spot spatial analysis to watershed-level NBs, considering hydrological characteristics. This method was applied to approximately 850 subwatersheds across the Republic of Korea, where land cover characteristics are complex. Reassessing nutrient budgets at the watershed scale, accounting for overlapping administrative boundary areas and crop cultivation ratios, indicated similar levels between the two methods. Hot spot analysis revealed that watersheds with elevated NBs mirrored the spatial patterns of livestock excreta and cropland. The spatial distribution characteristics of watersheds with high nutrient levels in rivers corresponded with the concentration characteristics of industrial and commercial areas. Therefore, applying watershed-level NBs based on land cover ratios that consider nutrient input characteristics in agricultural regions is deemed appropriate for selecting priority nutrient management areas. Collectively, this study presents a method for selecting nutrient management priority areas by simultaneously considering the spatial characteristics of various environmental factors, such as land cover, livestock excreta, river water quality, and land area-based watershed-specific NBs. The proposed approach, considering mixed land cover characteristics, is anticipated to be valuable for selecting priority management areas in watersheds with diverse pollution sources. Future research is needed to explore nutrient budgets within watersheds, the influence of land use on pollution sources, and their correlation with water quality.

Impact assessment of on-site swine wastewater treatment facilities on spatiotemporal variations of nitrogen loading in an intensive livestock farming watershed.

Excess nitrogen (N) resulting from human activity causes environmental issues, including eutrophication in agricultural watersheds with intensive livestock farming. Among the N sources in Korea, on-site swine wastewater treatment facilities (OSWTFs) tend to be densely distributed in watersheds with intensive livestock farming. Therefore, it is critical to sustainably manage livestock excreta. This study used the Soil and Water Assessment Tool (SWAT) to investigate the effects of various pollution sources, including OSWTFs, on N loads in rivers in the Cheongmi watershed, which is an intensive livestock farming and agricultural area in Korea. The simulated hydrological and water quality outputs were calibrated and validated for 2012-2019 using Sequential Uncertainty Fitting ver. 2 in the SWAT-Calibration and Uncertainty Program. The hydrological simulations agreed with the observations, with a correlation coefficient (R2) of ≥ 0.8 and Nash-Sutcliffe coefficient of 0.67-0.86. The simulated total N (TN) was also strongly correlated with the observed monthly average loading (R2, 0.36-0.73) and annual average concentration (R2 ≥ 0.5), demonstrating the reliability of the model constructed herein. A simulation of management scenarios indicates that, if the permissible N concentration in effluent from OSWTFs was reduced to 60 mg N/L, the TN concentrations in rivers would decrease by up to 50%. The findings of this study indicate that more stringent effluent water quality standards are required for OSWTFs to protect water quality and aquatic ecosystems in intensive swine farming watersheds.

Concentrations and Risk Assessments of Antibiotics in an Urban-Rural Complex Watershed with Intensive Livestock Farming.

Antibiotics used for the treatment of humans and livestock are released into the environment, whereby they pose a grave threat to biota (including humans) as they can cause the emergence of various strains of resistant bacteria. An improved understanding of antibiotics in the environment is thus vital for appropriate management and mitigation. Herein, surface water and groundwater samples containing antibiotics were analyzed in an urban-rural complex watershed (Cheongmi Stream) comprising intensive livestock farms by collecting samples across different time points and locations. The spatiotemporal trends of the residual antibiotics were analyzed, and ecological and antibiotic resistance-based risk assessments were performed considering their concentrations. The results showed that the concentrations and detection frequencies of the residual antibiotics in the surface water were affected by various factors such as agricultural activities and point sources, and were higher than those found in groundwater; however, frequent detection of antibiotics in groundwater showed that residual antibiotics were influenced by factors such as usage pattern and sewage runoff. Furthermore, few antibiotics posed ecological risks. The risk assessment methods adopted in this study can be applied elsewhere, and the results can be considered in the environmental management of residual antibiotics in the Cheongmi Stream watershed.

Strong links between load and manure and a comprehensive risk assessment of veterinary antibiotics with low KOW in intensive livestock farming watersheds.

Various veterinary antibiotics (VAs) are used in large quantities as an essential component for intensive livestock farming, and can flow into the environment from various pollution sources. In this study, VAs in surface water and groundwater in the Gwangcheon stream watershed, an intensive livestock farming area in Korea, were analyzed using ultra-high-performance liquid chromatograph-quadrupole orbitrap high-resolution mass spectrometer with online solid phase extraction. Although the selected VAs are relatively mobile and have low KOW values it is significant to assess their fates and ecological risks in the environment. The concentration of VAs in the surface water was higher than that in groundwater by approximately 23-fold, indicating that the former were directly introduced from pollution sources such as livestock manure. An analysis of the correlation between livestock manure production and the residuals of VAs in the stream showed a high linearity (R2 > 0.70), confirming that livestock excreta significantly contributed to the VAs in the watershed. A combined evaluation of environmental behaviors and ecological risks of VAs was performed for the first time using persistence, bioaccumulation potential, and toxicity properties and risk quotient values of VAs. Trimethoprim showed persistence and a potential impact on the ecosystem. The cumulative risk quotient values at one sampling point exceeded 1 indicating that several VAs can cumulatively cause local risk. The risk assessment method considering pollution sources, different locations, and correlation analysis applied in this study will be useful in evaluating the impacts of trace pollutants in watersheds.

Identifying nitrogen sources in intensive livestock farming watershed with swine excreta treatment facility using dual ammonium (δ15NNH4) and nitrate (δ15NNO3) nitrogen isotope ratios axes.

We proposed a novel approach based on dual ammonium and nitrate nitrogen isotope ratios (δ15NNH4 and δ15NNO3, respectively) axes to identify nitrogen sources in intensive livestock farming watersheds, especially those with swine excreta treatment facilities. The δ15NNH4 and δ15NNO3 values in water samples were measured monthly in 2016-2017. Soil and mineral fertilizers, sewage, sewage effluent, manure, and swine effluents were the five sources considered to identify nitrogen sources. The results showed that nitrogen pollution from agricultural activities was well reflected by the seasonal δ15NNH4 and δ15NNO3 patterns in the river, and microbial nitrification was suggested as the dominant nitrogen transformation process in the river. This study revealed that δ15NNH4 and δ15NNO3 axes provided better results than the traditionally used nitrate oxygen (δ18ONO3) and δ15NNO3 axes for identifying nitrogen sources in agricultural watersheds with swine excreta treatment facilities. The mixing model results showed that stream water was severely contaminated with swine effluents (e.g., a mean minimum contribution of 31%), thus affecting the quality of the mainstream (p = 0.068 < 0.10). This study was the first successful application of dual δ15NNH4 and δ15NNO3 axes to better understand nitrogen sources in intensive livestock farming watersheds with swine excreta treatment facilities.

Characteristics of veterinary antibiotics in intensive livestock farming watersheds with different liquid manure application programs using UHPLC-q-orbitrap HRMS combined with on-line SPE.

Composted livestock manures, in both solid and liquid form, are used as fertilizers in cropland. However, excess solid and liquid manures in agricultural watersheds are considered as nonpoint pollution sources because of their high nutrient and heavy metal contents of, as well as their antibiotic contents, especially veterinary antibiotics (VAs). In this study, 21 VAs under nine classes (i.e., cephems, ionophores, lincosamides, penicillins, pleuromutilins, quinolones, streptogramins, sulfonamides, and tetracyclines) found in agricultural watersheds were simultaneously analyzed via UHPLC-q-orbitrap high-resolution mass spectrometry using an on-line solid-phase extraction system. The residues of VAs in the surface water of two intensive livestock rearing watersheds (Cheongmi and Gwangcheon streams) in Korea were successfully quantified, and the values were found to range from 1.84 ± 0.42 ng L-1 to 835.6 ± 31.9 ng L-1. Time lags of 2-3 months were observed between the periods of liquid manure application and the periods with the maximum concentrations of VAs. In both watersheds, samples from points close to areas with extensive application of liquid manure exhibited high concentrations of most of the 21 VAs. Between the watersheds, the one with heavier application of liquid manure showed higher concentrations of the target VAs. To the best of our knowledge, this study represents the first attempt at evaluating the correlation between liquid manure application and environmental occurrence of VAs in surface water. The findings reveal that liquid manure application plays an important role in introducing VAs into aquatic environments.

A review of analytical procedures for the simultaneous determination of medically important veterinary antibiotics in environmental water: Sample preparation, liquid chromatography, and mass spectrometry.

Medically important (MI) antibiotics are defined by the United States Food and Drug Administration as drugs containing certain active antimicrobial ingredients that are used for the treatment of human diseases or enteric pathogens causing food-borne diseases. The presence of MI antibiotic residues in environmental water is a major concern for both aquatic ecosystems and public health, particularly because of their potential to contribute to the development of antimicrobial-resistant microorganisms. In this article, we present a review of global trends in the sales of veterinary MI antibiotics and the analytical methodologies used for the simultaneous determination of antibiotic residues in environmental water. According to recently published government reports, sales volumes have increased steadily, despite many countries having adopted strategies for reducing the consumption of antibiotics. Global attention needs to be directed urgently at establishing new management strategies for reducing the use of MI antimicrobial products in the livestock industry. The development of standardized analytical methods for the detection of multiple residues is required to monitor and understand the fate of antibiotics in the environment. Simultaneous analyses of antibiotics have mostly been conducted using high-performance liquid chromatography-tandem mass spectrometry with a solid-phase extraction (SPE) pretreatment step. Currently, on-line SPE protocols are used for the rapid and sensitive detection of antibiotics in water samples. On-line detection protocols must be established for the monitoring and screening of unknown metabolites and transformation products of antibiotics in environmental water.

Determination of 18 veterinary antibiotics in environmental water using high-performance liquid chromatography-q-orbitrap combined with on-line solid-phase extraction.

The use of antibiotics and their occurrence in the environment have received significant attention in recent years owing to the generation of antibiotic-resistant bacteria. Antibiotic residues in water near livestock farming areas should be monitored to establish effective strategies for reducing the use of veterinary antibiotics. However, environmental water contamination resulting from veterinary antibiotics has not been studied extensively. In this work, we developed an analytical method for the simultaneous determination of multiple classes of veterinary antibiotic residues in environmental water using on-line solid-phase extraction (SPE)-high performance liquid chromatography (HPLC)-high resolution mass spectrometry (HRMS). Eighteen popular antibiotics (eight classes) were selected as target analytes based on veterinary antibiotics sales in South Korea in 2015. The developed method was validated by calibration-curve linearities, precisions, relative recoveries, and method detection limits (MDLs)/limits of quantification (LOQs) of the selected antibiotics, and applied to the analysis of environmental water samples (groundwater, river water, and wastewater-treatment-plant effluent). All calibration curves exhibited r2 > 0.995 with MDLs ranging from 0.2 to 11.9 ng/L. Relative recoveries were between 50 and 150% with coefficients of variation below 20% for all analytes (spiked at 500 ng/L) in groundwater and river water samples. Relative standard deviations (RSDs) of standard-spiked samples were lower than 7% for all antibiotics. The on-line SPE system eliminates human-based SPE errors and affords excellent method reproducibility. Amoxicillin, ampicillin, clopidol, fenbendazole, flumequine, lincomycin, sulfadiazine, and trimethoprim were detected in environmental water samples in concentrations ranging from 1.26 to 127.49 ng/L. The developed method is a reliable analytical technique for the potential routine monitoring of veterinary antibiotics.

Assessment and identification of nitrogen pollution sources in the Cheongmi River with intensive livestock farming areas, Korea.

This study aimed to develop methods for assessing and identifying nitrogen sources in the Cheongmi River, Korea, that has intensive livestock farming areas (ILFA) in its watershed. The assessment focused on the feasibility of the simultaneous use of stable isotopic compositions of ammonium (δ15NNH4) and nitrate (δ15NNO3) for identifying the main nitrogen pollution sources in the Cheongmi River watershed. Our results suggested that the organic nitrogen (Org-N) to total nitrogen (T-N) ratio could be used as an indicator for assessing the effect of livestock excreta on waterways in ILFA. We observed that the T-N concentration was much more strongly affected by livestock excreta than the T-P concentration in the mainstream of the Cheongmi River. The positive correlation was more significant between δ15NNH4 and NH4-N than that between δ15NNO3 and NO3-N for river water samples. Furthermore, the use of δ15NNH4 was more effective than that of δ15NNO3 in evaluating nitrogen variations between May and August in the Cheongmi River because the differences in δ15NNH4 between May and August were more remarkable compared to those in δ15NNO3. Finally, the simultaneous use of δ15NNH4 and δ15NNO3 showed that the dominant nitrogen source at sites M3, M4, M5, and M6, specifically in May, was livestock excreta in the Cheongmi River. The results of this study could be used for sustainable water quality management in the Cheongmi River watershed.