Separately tracking the sources of hydrophobic and hydrophilic dissolved organic matter during a storm event in an agricultural watershed.

The hydrophobicity of dissolved organic matter (DOM) affects various aspects of its environmental impacts in terms of water quality, sorption behaviors, interactions with other pollutants, and water treatment efficiency. In this study, source tracking of river DOM was conducted separately for hydrophobic acid (HoA-DOM) and hydrophilic (Hi-DOM) fractions using end-member mixing analysis (EMMA) in an agricultural watershed during a storm event. EMMA with optical indices of bulk DOM revealed larger contributions of soil (24 %), compost (28 %), and wastewater effluent (23 %) to riverine DOM under high versus low flow conditions. Molecular level analysis of bulk DOM revealed more dynamic features, showing an abundance of CHO and CHOS formulae in riverine DOM under high- and low flow conditions. CHO formulae originated from soil (78 %) and leaves (75 %) and contributed to the increasing CHO abundance during the storm event, whereas CHOS formulae likely originated from compost (48 %) and wastewater effluent (41 %). The characterization of bulk DOM at the molecular level demonstrated that soil and leaves are the dominant contributors for the high-flow samples. However, in contrast to the results of bulk DOM analysis, EMMA with HoA-DOM and Hi-DOM revealed major contributions from manure (37 %) and leaf DOM (48 %) during storm events, respectively. The results of this study highlight the importance of individual source tracking of HoA-DOM and Hi-DOM for the proper evaluation of the ultimate roles of DOM in affecting river water quality and for a better understanding of DOM dynamics and transformation in natural and engineered systems.

Optical and molecular indices of dissolved organic matter for estimating biodegradability and resulting carbon dioxide production in inland waters: A review.

Biodegradable dissolved organic carbon (BDOC) constitutes the most labile fraction of dissolved organic matter (DOM), which also functions as a source of CO2 emissions from inland waters. However, no systematic review is available on DOM indicators of BDOC and CO2 production potential. Optical and molecular indices can be used to track small changes in DOM composition during biodegradation. In this review, we identified four different methods for measuring BDOC together with their strengths and limitations. In addition, we discuss the potential of using documented optical indices based on absorption and fluorescence spectroscopy and molecular indices based on Fourier transform ion cyclotron mass spectrometry as proxies for estimating BDOC and biodegradation-induced CO2 production based on previously reported relationships in the literature. Many absorbance- and fluorescence-based indices showed inconsistent relationships with BDOC depending on watershed characteristics, hydrology, and anthropogenic impacts. Nevertheless, several indices, including specific UV absorbance at 254 nm (SUVA254), humification index (HIX), and terrestrial humic-like fluorescent DOM (FDOM) components, tended to have negative relationships with BDOC in tropical and temperate watersheds under baseflow or drought periods. Protein-like FDOM exhibited the strongest correlation with BDOC in different systems, except during storms and flood events. Despite the limited number of studies, DOM molecular indices exhibited consistent relationships with BDOC, suggesting that the relative abundance of aliphatic formulas and the molecular lability index could act as reliable proxies. The DOM optical indices explain up to 96% and 78% variability in BDOC and CO2, respectively; nonetheless, there were limited studies on molecular indices, which explain up to 74% variability in BDOC. Based on literature survey, we recommend several sensitive indices such as SUVA254, HIX, and terrestrial humic- and protein-like FDOM, which could be useful indicators of BDOC and dissolved CO2 in inland water. Future research should incorporate a wider range of geographic regions with various land use, hydrology, and anthropogenic disturbances to develop system- or condition-specific DOM optical or molecular proxies for better prediction of BDOC and CO2 emissions.

A review on enhanced microplastics derived from biomedical waste during the COVID-19 pandemic with its toxicity, health risks, and biomarkers.

The COVID-19 pandemic led to the explosion of biomedical waste, a global challenge to public health and the environment. Biomedical waste comprising plastic can convert into microplastics (MPs, < 5 mm) by sunlight, wave, oxidative and thermal processes, and biodegradation. MPs with additives and contaminants such as metals are also hazardous to many aquatic and terrestrial organisms, including humans. Bioaccumulation of MPs in organisms often transfers across the trophic level in the global food web. Thus, this article aims to provide a literature review on the source, quantity, and fate of biomedical waste, along with the recent surge of MPs and their adverse impact on aquatic and terrestrial organisms. MPs intake (ingestion, inhalation, and dermal contact) in humans causing various chronic diseases involving multiple organs in digestive, respiratory, and reproductive systems are surveyed, which have been reviewed barely. There is an urgent need to control and manage biomedical waste to shrink MPs pollution for reducing environmental and human health risks.

Change in adsorption behavior of aquatic humic substances on microplastic through biotic and abiotic aging processes.

Interactions between microplastics (MPs) and humic substances (HS) are inevitable in MP-contaminated aquatic environment because of the ubiquitous presence of HS. In this study, we explored the effects of abiotic and biotic aging processes on the adsorption behavior of aquatic HS on MPs. Aging experiments were conducted using polyethylene (PE) as a representative MP, in which UV irradiation and microbial incubation were applied for 15 to 18 days to mimic the natural abiotic and biotic aging processes. Surface modifications after the aging treatments were evidenced by the appearance of CO, CO, O-C=O, and -OH groups; the formation of grooves on UV-aged PE; and the formation of biofilms on the surface of bio-aged PE. The specific surface areas of both treated PE MPs increased with aging. Higher HS adsorption on PE surface was observed after the aging treatments, with a highest kinetic rate for UV-aged PE than that for bio-aged PE. The adsorption isotherm models revealed that the aging processes enhanced the HS adsorption tendency, as evidenced by the highest adsorption capacity for UV-aged PE (~187 µg C/m2), followed by bio-aged PE (~157 µg C/m2) and pristine PE (~87.5 µg C/m2) for a comparable extended aging period (15-18 days). The difference was more pronounced at a lower pH. The enhanced HS adsorption was mainly attributed to the formation of hydrogen bonds, whereas HS adsorption on pristine PE was dominated by hydrophobic interactions and weak van der Waals interactions. Among the two identified fluorescent components (terrestrial humic-like C1 and protein-like C2), C1 exhibited a higher affinity for adsorption onto PE irrespective of aging. Our findings provide insights into the substantial changes that occur in the interactions between MPs and aquatic organic matter with aging processes, which may alter the fate and environmental impacts of MPs in many aquatic systems.

Source tracking of dissolved organic nitrogen at the molecular level during storm events in an agricultural watershed.

Accelerated export of nitrogen-containing dissolved organic matter (DOM) or dissolved organic nitrogen (DON) to streams and rivers from agricultural watersheds has been reported worldwide. However, few studies have examined the dynamics of DOM molecular composition with the attention paid to the relative contributions of DON from various sources altered with flow conditions. In this study, end-member mixing analysis (EMMA) was conducted with the optical properties of DOM to quantify the relative contributions of several major organic matter sources (litter, reed, field soil, and manure) in two rivers of a small agricultural watershed. DOC and DON concentration increased during the storm events with an input of allochthonous DOM as indicated by an increase in specific ultraviolet absorbance at 254 nm (SUVA254) and a decrease in biological index (BIX), fluorescence index (FI), and protein-like component (%C3) at high discharge. EMMA results based on a Bayesian mixing model using stable isotope analysis in R (SIAR) were more accurate in source tracking than those using the traditional IsoSource program. Manure (>30%) and field soil (also termed as "manure-impacted field soil") (>23%) end-members revealed their predominant contributions to the riverine DOM in SIAR model, which was enhanced during the storm event (up to 56% and 38%, respectively). The molecular composition of the riverine DOM exhibited a distinct footprint from the manure and manure-impacted field soil, with a larger number of CHON formulas and abundant polyphenols and condensed aromatics in peak flow samples in the studied rivers. The riverine DOM during peak flow contained many unique molecular formulas in both rivers (4980 and 2082) of which >60% originated from manure and manure-impacted field soil. Combining the EMMA with DOM molecular composition clearly demonstrated the effect of manure fertilizer on the riverine DOM of the watershed with intensive agriculture. This study provides insights into the source tracking and regulation of DON leaching from anthropogenically altered river systems worldwide.

Reassessing riverine carbon dioxide emissions from the Indian subcontinent.

Anthropogenic perturbations are increasing uncertainties in estimating CO2 emissions via air-water CO2 flux (FCO2) from large rivers of the Indian subcontinent. This study aimed to provide an improved estimate of the total FCO2 from the subcontinental rivers by combining calculations of the partial pressure of CO2 (pCO2) in eight major rivers with new measurements in the Ganges and Godavari. The average pCO2 in the two newly surveyed rivers, including tributaries, wastewater drains, and impoundments, were 3-6 times greater than the previously reported values. In some highly polluted urban tributaries and middle reaches of the Ganges that drain metropolitan areas, the measured pCO2 exceeded 20,000 µatm, ~40 times the background levels of the headwaters originating in the carbonate-rich Himalayas. The high pCO2 above 28,000 µatm in the lower reach of the Godavari was seven times the moderate levels of pCO2 in the headwaters of the volcanic Deccan Traps, indicating enhanced CO2 production in soils and anthropogenic sources under favorable conditions for organic matter degradation. Across the northern rivers, pCO2 exhibited a significant negative relationship with dissolved oxygen, but a positive relationship with inorganic N or P concentrations. The strong influence of water pollution on riverine pCO2 suggests that CO2 emissions from hypoxic, eutrophic reaches can greatly exceed phytoplanktonic CO2 uptake. Spatially resolved pCO2 data, combined with three gas transfer velocity estimates, provided a higher range of FCO2 from the subcontinental rivers (100.9-130.2 Tg CO2 yr-1) than the previous estimates (7.5-61.2 Tg CO2 yr-1). The revised estimates representing 2-5% of the global riverine FCO2 illustrate the importance of the Indian subcontinental rivers under increasing anthropogenic pressures in constraining global inland waters FCO2.

Phytoplankton nutrient use and CO2 dynamics responding to long-term changes in riverine N and P availability.

Long-term trends in riverine nutrient availability have rarely been linked to both phytoplankton composition and functioning. To explore how the changing availability of N and P affects not only phytoplankton abundance and composition but also the resource use efficiency of N, P, and CO2, a 25-year time series of water quality in the lower Han River, Korea, was combined with additional measurements of riverine dissolved organic carbon (DOC) and CO2. Despite persistent eutrophication, recent decreases in P relative to N have been steep in the lowest reach, increasing the annual mean mass ratio of N to P (N/P) from 24 (1994-2015) to 65 (2016-2018). While Chl a and cyanobacterial abundance exhibited overall positive and inverse relationships with P concentrations and N/P, respectively, severe harmful algal blooms (HABs) concurred with short-term increases in P and temperature. Microcystis often dominated HABs at low N/P that usually favors N-fixing cyanobacteria such as Anabaena. In the middle and lower reaches, phytoplanktonic P use efficiency was typically lower at low N/P. V-shaped relationships between N/P and CO2 concentrations, together with longitudinal upward shifts in the inverse relationship between Chl a and CO2, implied that eutrophication-enhanced phytoplankton biomass could turn into a significant source of CO2. after passing a threshold. The combined results suggest that cyanobacterial dominance co-limited by P availability and temperature can lower planktonic P use efficiency, while enhancing riverine CO2 emissions at low N/P ratios.

Toxicity and biomarkers of micro-plastic in aquatic environment: a review.

Microplastics (MPs; <5 mm) are found in all aquatic environments. Due to harmful impacts, MPs pose a great threat to the aquatic ecology. Therefore, this review aims to provide an overview of the risk, bioavailability, and toxicity of MPs in aquatic organisms. Various factors affecting MPs bioavailability and level of risks at cellular and molecular level on aquatic organisms are comprehensively discussed. More specifically biomarkers for antioxidant response (superoxide dismutase, catalase, glutathione peroxidase, reductase, and glutathione S-transferase), neurotoxic impairment (acetylcholinesterase), lysosomal activity alteration, and genotoxicity have been discussed in detail. Biomarkers are powerful tool in the monitoring programme, but the collection of literature on biomarkers for MPs is limited. Thus, here we demonstrate how to evaluate MPs impact, in monitoring programme, on organisms using biomarkers in aquatic environment. This review would broaden the existing knowledge on the toxic effect and biomarkers of MPs and offer research priorities for future studies.

Synergistic effects of urban tributary mixing on dissolved organic matter biodegradation in an impounded river system.

Dams and wastewater may greatly perturb riverine fluxes of dissolved organic matter (DOM) and CO2, yet little is known about the relationships between altered DOM quality and CO2 emission in eutrophic impounded river systems. A basin-wide field survey of surface water CO2 and dissolved organic carbon (DOC) was combined with laboratory incubations to examine how dams and urban tributaries delivering treated wastewater influence longitudinal patterns in DOM properties and CO2 along the impounded Han River traversing Seoul metropolitan area. Fluorescent DOM indices including parallel factor analysis (PARAFAC) components were used to characterize DOM in relation to biodegradable DOC (BDOC). Compared with distinct downstream increases in DOC and CO2, BDOC concentration and its proportion in DOC (%BDOC) were highly variable along the mainstem and peaked at urban tributaries. Longitudinal increases in fluorescence index (FI), biological index (BIX), and two PARAFAC components (C2 and C3) contrasted with general decreases in humification index (HIX) and C1, reflecting increasing downstream inputs of anthropogenic DOM. During a 5-day incubation employing continuous CO2 measurements, the cumulative production of CO2 in the mainstem water mixed with urban tributary water was significantly higher than the level expected for conservative mixing of the two samples, indicating a synergistic enhancement of DOM biodegradation. Molecular formulas identified by Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) revealed more consumed molecules in the mainstem water and more newly produced molecules in the tributary water over the 5-day incubation, implying abundant labile components in the mainstem water discharged from the upstream dam and highly processed tributary DOM limited in immediately biodegradable organic materials. Downstream increases in CO2 and DOC along the Han River, combined with the synergistic effect observed in the mixed water, suggest that mixing wastewater-derived DOM with labile autochthonous DOM can enhance CO2 production in the river system perturbed by impoundment and wastewater.

CO2 Outgassing from an Urbanized River System Fueled by Wastewater Treatment Plant Effluents.

Continuous underway measurements were combined with a basin-scale survey to examine human impacts on CO2 outgassing in a highly urbanized river system in Korea. While the partial pressure of CO2 (pCO2) was measured at 15 sites using syringe equilibration, 3 cruises employing an equilibrator were done along a 30 km transect in the Seoul metropolitan area. The basin-scale survey revealed longitudinal increases in surface water pCO2 and dissolved organic carbon (DOC) in the downstream reach. Downstream increases in pCO2, DOC, fluorescence index, and inorganic N and P reflected disproportionately large contributions from wastewater treatment plant (WWTP) effluents carried by major urban tributaries. Cruise transects exhibited strong localized peaks of pCO2 up to 13 000 µatm and 13CO2 enrichment along the confluences of tributaries at an average flow, whereas CO2 pulses were dampened by increased flow during the monsoon period. Fluctuations in pCO2 along the eutrophic reach downstream of the confluences reflected environmental controls on the balance between photosynthesis, biodegradation, and outgassing. The results underscore WWTP effluents as an anthropogenic source of nutrients, DOC, and CO2 and their influences on algal blooms and associated C dynamics in eutrophic urbanized river systems, warranting further research on urbanization-induced perturbations to riverine metabolic processes and carbon fluxes.