Sedimentary spectrum and potential ecological risks of residual pharmaceuticals in relation to sediment-water partitioning and land uses in a watershed.

Pharmaceutical residues in river surficial sediment are prone to anthropogenic impacts and environmental factors in watershed, but the mechanisms remain unclear. This study attempted to reveal surficial sediment-water pseudo-partitioning and anthropogenic (land use) patterns of pharmaceutical residues in surficial sediment among 23 subwatersheds of Jiulong River, southeast China with a gradient of urban land use percentile in dry and wet seasons. Thirty-eight out of target 86 compounds from six-category pharmaceuticals were quantified and ranged from below the quantification limits (0.001 mg kg-1 dry mass) up to 8.19 mg kg-1 dry mass (chlortetracycline) using a developed SPE-HPLC-MS/MS protocol. Antibiotics and non-steroidal anti-inflammatory drugs (NSAIDs) collectively dominated sedimentary pharmaceutical residues for 34.5-99.8% of the total quantified compounds (median at 92%). Land uses in subwatersheds showed high consistency with sedimentary pharmaceutical residues in the dry season rather than the wet season, especially for human use only and veterinary use only compounds. Surficial sediment-water partitioning of pharmaceutical compounds influenced their sedimentary residues regardless of season, which were determined by properties of compound and surficial sediment interactively. All tetracycline compounds, trimethoprim (sulfonamides synergist), caffeine (central nervous system drug), and oxfendazole (antiparasitic drug) were quantified to pose high potential ecological risks to aquatics. Findings of this study suggest that pseudo-persistent legacy of human and veterinary pharmaceuticals requires a wider coverage of pharmaceutical compounds for a comprehensive ecological assessment in the environment and more involvement of anthropogenic impacts and socioeconomic factors in the future studies.

Modifying SWAT-CS for simulating chloride dynamics in a Boreal Shield headwater catchment in south-central Ontario, Canada.

Rising chloride concentrations in surface water due to applications of deicing practices is proving detrimental to aquatic systems. In this study, a new chloride module is developed for a version of the Soil and Water Assessment Tool specially designed for Canadian Shield catchments (SWAT-CS) to model long-term chloride dynamics in a headwater catchment in south-central Ontario, Canada. In this modified model (SWAT-CS-CL; extended SWAT-CS model for chloride), chloride sources, sinks, internal storages or pools, and movement between these components are depicted. Performance of SWAT-CS-CL is assessed using a two-stage evaluation process based on the generalized likelihood uncertainty analysis (GLUE) framework. SWAT-CS-CL was found to perform moderately well, with simulated monthly chloride in streams and lake outflow following overall chloride trends and capturing regular chloride dynamics. However, simulations fail to consistently reproduce some instances of large or low chloride fluxes. Limitations in simulating large chloride fluxes may be attributed to the inadequate ability for SWAT-CS-CL to closely simulate snowpack and snowmelt processes. Parameter transferability among sub-catchments does suggest that there is a potential to extend SWAT-CS-CL to other Canadian Shield catchments for chloride modelling. Further improvements are needed through more trials to other catchments in a same or different landscape, and by modifying the simulation structure, especially representation of snow hydrology and chloride inputs.

Spectrum and environmental risks of residual pharmaceuticals in stream water with emphasis on its relation to epidemic infectious disease and anthropogenic activity in watershed.

Pharmaceuticals vastly consumed by modern human for health and food might track anthropogenic impacts on aquatic ecosystem via their wide residual spectrum. This study investigated the spectrum of pharmaceutical residuals in stream water at confluence point of each subwatershed with various land use pattern in Jiulong River watershed, southeastern China. Stream water was sampled in both wet and dry seasons of 2016. Results showed that 59 out of the selected 94 compounds from 6 pharmaceutical categories were quantified among these stream water samples, up to 1488 ng L-1 for caffeine (CAF). Antibiotics and central nervous system drugs (CNs) collectively dominated the quantified instream pharmaceutical residuals. Outbreaks of epidemic infectious diseases for human and livestock partially but significantly matched seasonality of instream pharmaceutical residuals. Anthropogenic impact as land use composition of subwatersheds was significant on instream pharmaceutical loadings, especially urban land use. Cocktail risk of instream pharmaceutical residuals to aquatic organisms was assessed ranging from low to medium among the subwatersheds except high risk for the W-01 subwatershed in the dry season. Evidence from this study indicated that seasonality and wide spectrum of instream pharmaceutical residual determination could reveal anthropogenic impacts to aquatic ecosystem, such as epidemic disease and land use.

Losses of natural coastal wetlands by land conversion and ecological degradation in the urbanizing Chinese coast.

Coastal wetland ecosystems have experienced serious losses of area and ecological function and are currently facing worldwide challenges due to coastal development and global climate change. This study attempted to explore patterns and possible factors driving loss of natural coastal wetlands due to land conversion (permanent loss) and ecological degradation (temporal loss) in three urbanizing coastal city clusters, China in the period of 1990-2015. The natural coastal wetland area was substantially lost due to land conversion highly related to regional economic development. The ecological degradation, assessed as a function of surface water quality, resulted in much greater impairment area of natural coastal wetlands. This impairment was predominantly driven by inbound river pollutants' discharge, rather than local discharge. This study suggests that the ecological degradation should be considered as well as the land conversion loss for conserving the remaining natural coastal wetland ecosystems. The pollutant discharges from the inbound river watersheds need to be mitigated as the local discharges for reducing the functional degradation of the natural coastal wetlands while the regional economic development plan should consider the conservation needs of the remaining natural coastal wetlands worldwide.

Urbanization gradient of selected pharmaceuticals in surface water at a watershed scale.

Ubiquitous detection of pharmaceuticals in the aquatic environment around the world raises a great public concern. Aquatic residuals of pharmaceuticals have been assumed to relate to land use patterns and various human activities within a catchment or watershed. This study generated a gradient of human activity in the Jiulong River watershed, southeastern China by urban land use percentage in 20 research subwatersheds. Thirty-three compounds from three-category pharmaceuticals [26 compounds of 5 antibiotic groups, 6 compounds of non-steroidal anti-inflammatory drugs (NSAIDs), and 1 compound of respiratory system drugs (RSDs)] were quantified in stream water before the research subwatershed confluences with two sampling events in dry and wet seasons. In total, 27 out of the 33 pharmaceutical compounds of interest were found in stream waters. Seasonality of instream pharmaceuticals was observed, with less compounds and lower concentrations in the wet season sampling event than in the dry season one. Urban land use in the research subwatershed was identified as the main factor influencing in stream pharmaceutical concentrations and composition regardless of season. Rural land uses contributed a mixture of human and veterinary pharmaceuticals possibly from agricultural application of manure and sewage sludge and aquaculture in the research subwatersheds. Erythromycin in both sampling events showed medium to high risks to aquatic organisms. Results of this study suggest that urban pharmaceutical management, such as a strict prescription regulations and high-efficient removal of pharmaceuticals in wastewater treatment, is critical in reducing aquatic pharmaceutical loads.

Anthropogenic land uses elevate metal levels in stream water in an urbanizing watershed.

Land use/cover change is a dominant factor affecting surface water quality in rapidly developing areas of Asia. In this study we examined relationships between land use and instream metal loadings in a rapidly developing mixed land use watershed in southeastern China. Five developing subwatersheds and one forested reference site (head water) were instrumented with timing- and rainfall-triggered autosampler and instream loadings of anthropogenic metals (Cu, Zn, Pb, Cr, Cd, and Mn) were monitored from March 2012 to December 2013. Farm land and urban land were positively, and forest and green land were negatively associated with metal loadings (except Cr) in stream water. All developing sites had higher loadings than the reference head water site. Assessed by Chinese surface water quality standard (GB3830-2002), instream loadings of Cu and Zn occasionally exceeded the Class I thresholds at monitoring points within farmland dominated subwatersheds while Mn loadings were greater than the limit for drinking water sources at all monitoring points. Farm land use highly and positively contributed to statistical models of instream loadings of Cu, Zn, Cd, and Mn while urban land use was the dominant contributor to models of Pb and Cd loadings. Rainfall played a crucial role in metal loadings in stream water as a direct source (there were significant levels of Cu and Zn in rain water) and as a driver of watershed processes (loadings were higher in wet years and seasons). Urbanization effects on metal loadings in this watershed are likely to change rapidly with development in future years. Further monitoring to characterize these changes is clearly warranted and should help to develop plans to avoid conflicts between economic development and water quality degradation in this watershed and in watersheds throughout rapidly developing areas of Asia.

Occurrence and environmental implications of pharmaceuticals in Chinese municipal sewage sludge.

The presence of pharmaceuticals in aquatic environment has become a topic of concern because of their potential adverse effects on human health and wildlife species. A total of 45 dewatered sewage sludge samples were collected throughout China and analyzed for 30 commonly consumed pharmaceutical residues. Ofloxacin was found to be the dominant contaminant with concentrations up to 24760 µg kg(-1), followed by oxytetracycline (5280 µg kg(-1)), norfloxacin (5280 µg kg(-1)) and ketoprofen (4458 µg kg(-1)). The concentration of pharmaceutical residues varied greatly depending on the operation conditions of wastewater treatment plants and sampling locations. Poor agreement was found between the predicted (calculation based on the annual consumption and coefficient of sludge water partition) and detected concentrations of the pharmaceuticals indicating that the occurrence of pharmaceutical residues was affected by various factors such as loading rates, sewage properties and the chemical properties such as the contribution from polar groups. National wide fate and ecotoxicity study is required for the development of control strategies.

Pharmaceutical residues in tidal surface sediments of three rivers in southeastern China at detectable and measurable levels.

Pharmaceutical compounds were increasingly detected in environmental matrices but little is known whether these compounds would transport to coastal zones via watersheds. Three typical tidal rivers in southeastern China were selected and 15 surface sediment samples (0-10 cm) were collected along a 50-km tidal section of each river. Surface sediment samples were frozen-drying and then extracted for pharmaceutical compounds by an accelerated solvent extraction system. The pharmaceutical compounds in extracts were scanned using a high-performance liquid chromatography/tandern mass spectrometry (HPLC-MS/MS). Three hundred and thirty compounds from nine pharmaceutical groups were detected with signal-to-noise above three (detectable level) in the surface sediments, of which 186 compounds were with a signal-to-noise above ten (measurable level). Of all, 291 and 80 compounds were detectable and measurable in all the three rivers, respectively. The Jiulong River showed a high load of pharmaceutical compounds in surface sediment than other two rivers. Of the nine pharmaceutical groups, the antihistamines and detoxification group and anti-infective drug group contributed five dominant compounds in the surface sediments in all the three rivers. Natures of pharmaceutical compounds rather than the sediment properties (pH, EC, and total carbon content) might influence their residues. The incredible number and intensity of pharmaceutical residues were detected in tidal surface sediments of the three rivers indicating that the pharmaceutical contamination should be strongly considered in China. Source identification and eco-toxicity assessment should be taken into account in the future study. Therapeutic medicine managements need to be strictly improved at a watershed scale to reduce loads of pharmaceuticals into aquatic ecosystems.