Key factors driving dissolved organic matter composition and bioavailability in lakes situated along the Eastern Route of the South-to-North Water Diversion Project, China.

The Eastern Route of the South-to-North Water Diversion Project (SNWDP-ER) is a large scale multi-decade infrastructure project aiming to divert substantial amounts of water (≈45 billion m3 yr-1) to alleviate water shortage in comparatively arid regions of northern China. The project has ramifications for hydrological connectivity and biogeochemical cycling of dissolved organic matter (DOM) in regional lakes affected by the project. We carried out an extensive field sampling campaign along the SNWDP-ER in different hydrological seasons of 2018 and monthly observations in Lake Hongze and Lake Luoma from April 2018 to June 2021. We found the lakes connecting to the SNWDP-ER had higher mean DOC, specific UV absorbance, higher ratio of humic-like to protein-like fluorophores (Humic : Protein), and shallower spectral slope (S275-295) in the wet season compared to the wet-to-dry transition, and dry seasons. The southern lakes and Yangtze River had lower DOC concentration, bioavailable DOC (BDOC), and higher DOM aromaticity compared to the northern two downstream lakes. Ultrahigh-resolution mass spectrometry (FT-ICR MS) revealed higher relative abundance of CHO-containing and aromatic compounds in the Yangtze River and the southern three upstream lakes compared to the northern two lakes. The data from Lake Hongze and Lake Luoma, studied in different hydrological seasons, suggest that water delivery had high consistency in DOM composition and BDOC over the season. We conclude that positioning along the watercourse and seasonally variable hydrological conditions play an important role in influencing the DOM composition and bioavailability of key lakes connecting to the SNWDP-ER. Our results indicated that the water diversion project delivers water with low DOC concentration and higher aromaticity and thus is of higher quality since it has higher DOM removal potential during drinking water treatment.

Rainstorms drive export of aromatic and concurrent bio-labile organic matter to a large eutrophic lake and its major tributaries.

Lakes are hotspots for global carbon cycling, yet few studies have explored how rainstorms alter the flux, composition, and bio-lability of dissolved organic matter (DOM) in inflowing rivers using high-frequency monitoring. We conducted extensive campaigns in the watershed of Lake Taihu and made daily observations for three years in its two largest inflowing tributaries, River Dapu and River Yincun. We found higher DOC, bio-labile DOC (BDOC), and specific UV absorbance (SUVA254) levels in the northwestern inflowing regions compared with the remaining lake regions. DOC and BDOC increased during rainstorms in River Dapu, and DOC declined due to local dilution and BDOC increased during rainstorms in River Yincun. We found that rainstorms resulted in increased DOM absorbance a350, SUVA254, and humification index (HIX) and enhanced percentages of humic-like fluorescent components, %polycyclic condensed aromatic and %polyphenolic compounds as revealed from ultrahigh-resolution mass spectrometry (FT-ICR MS), while spectral slope (S275-295) and the percentages of protein-like C1 and C3 declined during rainstorms compared with other seasons. This can be explained by a combined flushing of catchment soil organic matter and household effluents. The annual inflows of DOC and BDOC to Lake Taihu were 1.15 ± 0.18 × 104 t C yr-1 and 0.23 ± 0.06 × 104 t C yr-1 from River Dapu and 2.92 ± 0.42 × 103 t C yr-1 and 0.53 ± 0.07 × 103 t C yr-1 from River Yincun, respectively, and the fluxes of DOC and BDOC from both rivers increased during rainstorms. We found an elevated frequency of heavy rainfall and rainstorms in the lake watershed during the past six decades. We conclude that an elevated input of terrestrial organic-rich DOM with concurrent high aromaticity and high bio-lability from inflowing rivers is likely to occur in a future wetter climate.

Changes in Water Chemistry Associated with Rainstorm Events Increase Carbon Emissions from the Inflowing River Mouth of a Major Drinking Water Reservoir.

Large reservoirs are hotspots for carbon emissions, and the continued input and decomposition of terrestrial dissolved organic matter (DOM) from upstream catchments is an important source of carbon emissions. Rainstorm events can cause a surge in DOM input; however, periodic sampling often fails to fully capture the impact of these discrete rainstorm events on carbon emissions. We conducted a set of frequent observations prior to and following a rainstorm event in a major reservoir Lake Qiandao (China; 580 km2) from June to July 2021 to investigate how rainstorms alter water chemistry and CO2 and CH4 emissions. We found that the mean CO2 efflux (FCO2) (13.2 ± 9.3 mmol m-2 d-1) and CH4 efflux (FCH4) (0.12 ± 0.02 mmol m-2 d-1) in the postrainstorm campaign were significantly higher than those in the prerainstorm campaign (-3.8 ± 3.0 and +0.06 ± 0.02 mmol m-2 d-1, respectively). FCO2 and FCH4 increased with increasing nitrogen and phosphorus levels, elevated DOM absorption (a350), specific UV absorbance SUVA254, and terrestrial humic-like fluorescence. Furthermore, FCO2 and FCH4 decreased with increasing chlorophyll-a (Chl-a), dissolved oxygen (DO), and pH. A five-day laboratory anoxic bioincubation experiment further revealed a depletion of terrestrial-DOM concurrent with increased CO2 and CH4 production. We conclude that rainstorms boost the emission of CO2 and CH4 fueled by the surge and decomposition of fresh terrestrially derived biolabile DOM in this and likely many other reservoir's major inflowing river mouths.

Unified understanding of intrinsic and extrinsic controls of dissolved organic carbon reactivity in aquatic ecosystems.

Despite our growing understanding of the global carbon cycle, scientific consensus on the drivers and mechanisms that control dissolved organic carbon (DOC) turnover in aquatic systems is lacking, hampered by the mismatch between research that approaches DOC reactivity from either intrinsic (inherent chemical properties) or extrinsic (environmental context) perspectives. Here we propose a conceptual view of DOC reactivity in which the combination of intrinsic and extrinsic factors controls turnover rates and determines which reactions will occur. We review three major types of reactions (biological, photochemical, and flocculation) from an intrinsic chemical perspective and further define the environmental features that modulate the expression of chemically inherent reactivity potential. Finally, we propose hypotheses of how extrinsic and intrinsic factors together shape patterns in DOC turnover across the land-to-ocean continuum, underscoring that there is no intrinsic DOC reactivity without environmental context. By acknowledging the intrinsic-extrinsic control duality, our framework intends to foster improved modeling of DOC reactivity and its impact on ecosystem services.

Unraveling the Role of Anthropogenic and Natural Drivers in Shaping the Molecular Composition and Biolability of Dissolved Organic Matter in Non-pristine Lakes.

Lakes receive and actively process terrestrial dissolved organic matter (DOM) and play an important role in the global carbon cycle. Urbanization results in elevated inputs of nonpoint-source DOM to headwater streams. Retention of water in lakes allows time for alteration and transformation of the chemical composition of DOM by microbes and UV radiation. Yet, it remains unclear how anthropogenic and natural drivers impact the composition and biolability of DOM in non-pristine lakes. We used optical spectroscopy, Fourier transform ion cyclotron mass spectrometry, stable isotopic measurements, and laboratory bioincubations to investigate the chemical composition and biolability of DOM across two large data sets of lakes associated with a large gradient of urbanization in lowland Eastern China, encompassing a total of 99 lakes. We found that increased urban land use, gross domestic products, and population density in the catchment were associated with an elevated trophic level index, higher chlorophyll-a, higher bacterial abundance, and a higher amount of organic carbon with proportionally higher contribution of aliphatic and peptide-like DOM fractions, which can be highly biolabile. Catchment areas, water depth, lake area: catchment area, gross primary productivity, δ18O-H2O, and bacterial abundance, however, had comparatively little linkage with DOM composition and biolability. Urban land use is currently intensifying in many developing countries, and our results anticipate an increase in the level of biolabile aliphatic DOM from nonpoint sources and accelerated carbon cycling in lake ecosystems in such regions.

Organic Matter Degradation across Ecosystem Boundaries: The Need for a Unified Conceptualization.

The global carbon cycle connects organic matter (OM) pools in soil, freshwater, and marine ecosystems with the atmosphere, thereby regulating their size and reactivity. Due to the complexity of biogeochemical processes and historically compartmentalized disciplines, ecosystem-specific conceptualizations of OM degradation have emerged independently of developments in other ecosystems. Recent discussions regarding the relative importance of molecular composition and ecosystem properties on OM degradation have diverged in opposing directions across subdisciplines, leaving our understanding inconsistent. Ecosystem-dependent theories are problematic since properties unique to an ecosystem may change in response to anthropogenic stressors, including climate change. The next breakthrough in our understanding of OM degradation requires a shift in focus towards developing a unified theory of controls on OM across ecosystems.

Rainstorm events shift the molecular composition and export of dissolved organic matter in a large drinking water reservoir in China: High frequency buoys and field observations.

Rainstorm events can flush large amounts of terrestrial organic-rich material into lakes that are used for drinking water. To date, few studies have been carried out to investigate how rainstorm events change the molecular composition, bio-lability, and flux of upstream-imported dissolved organic matter (DOM), which can impact the odor and taste of drinking water as well as the efficiency of wastewater treatment. We undertook high-frequency buoy monitoring and point sample collection (n = 495), during high, moderate, and low inflow discharge, in Lake Qiandao, a key drinking water source for about 10 million people. Data from two online fluorescent DOM sensors deployed and field samples collected at the river site, Jiekou, and the lake site, Xiaojinshan, showed that rainstorm events increased the specific UV absorbance (SUVA254), humification index (HIX), humic-like components (C1-C2), and FT-ICR MS derived condensed aromatic and polyphenolic compounds (p < 0.001) and decreased the spectral slope of DOM (S275-295), spectral slope ratio (SR), biological index (BIX), and highly bio-degradable peptide-like and aliphatic substances (p < 0.001). Our results suggest that rainstorm events enhanced the export to the lake of colored, hydrophobic, and aromatic DOM. Upstream-derived dissolved organic carbon (DOC) concentrations decreased (p < 0.001), while DOC bio-availability (BDOC) increased only slightly (p < 0.05) during rainstorm events. The loss rate of DOC in Lake Qiandao is 0.82 × 104 t C yr-1, of which 0.30 × 104 t C yr-1 is highly bio-labile, and higher occurrences of both ≥ 25 mm d - 1 and ≥ 50 mm d - 1 rainfall events are anticipated by linear fittings for this region in the future. The application of in situ fluorescence sensors provides an early warning of DOC surge incidents caused by rainstorm events and may be useful in advising drinking water treatment plant managers of changes in raw water DOM quality and treatability.

Rice-paddy field acts as a buffer system to decrease the terrestrial characteristics of dissolved organic matter exported from a typical small agricultural watershed in the Three Gorges Reservoir Area, China.

Agricultural watersheds are a crucial contributor of terrestrial dissolved organic matter (DOM) for the adjacent aquatic environment. Recently, ecological engineering of the buffer zone such as a rice-paddy field was established to reduce the export of nutrients and contaminants from a small agricultural watershed. However, the potential of the rice-paddy field to reduce the terrestrial signature of DOM is unclear. Therefore, two small agricultural sub-catchments (i.e., sub-1 and sub-2) with different land uses and hill slope angles in the Three Gorges Reservoir (TGR) area of China were studied from 2014 to 2015. The results showed that the terrestrial DOM signals are indicated by optical indices (SUVA254, SR, fluorescence index) in the steeper and more forest covered, but rice-paddy field buffered sub-catchment (i.e., sub-2) decreased significantly, as compared to the reference sub-catchment (i.e., sub-1). Regardless of seasonal variations, the rice-paddy field retained a buffering role to reduce the terrestrial property of DOM and the highest capacity was observed during the rice-growth period. However, during storm events, the differences of DOM properties for two sub-catchments were not significant, because the buffer system was weakened. Finally, environmental implications of the role of such a buffer zone in the TGR areas are discussed. These results demonstrate that rice-paddy fields are successful in mitigating the terrestrial property of exported DOM, but the weaker performance during storm events still needs to be considered.

Selective removal of dissolved organic matter affects the production and speciation of disinfection byproducts.

The heterogeneity of dissolved organic matter (DOM) in natural and human impacted waters and the variety of drinking water treatment processes employed has made a mechanistic understanding of disinfection byproduct (DBP) formation challenging. In this study, we examined the formation of the regulated DBPs (Trichloromethanes, THM, and Haloacetic acids, HAA) during full-scale water treatment operations both with prechlorination treatment (normal operations for the drinking water plant) and without (altered operations); followed by coagulation, flocculation, filtration, and chlorination. The source water DOM concentration ranged 6.4 to 7.3 mg-C/L. DOM composition was moderately humic and degraded with a mix of microbial- and terrestrial-like characteristics. Removal of raw water prechlorination caused an average reduction in total THM and HAA concentrations of 52.7% and 40.0%, respectively, with the greater reduction noted for chlorinated-DBPs rather than brominated-DBPs. Prechlorination treatment resulted in a higher relative production of Cl3CH and BrCl2CH associated with aromatic, humic, and terrestrial-like DOM. Without prechlorination, the DBP pool had higher proportions of brominated-DBPs (Br3CH, Br2ClCH, Br2CHCOOH, BrClCHCOOH, and BrCH2COOH) associated with microbial-like, processed humic-like, and protein-like DOM. These observed patterns could not be explained by chloride demand and DOM concentration, indicating that DOM composition played an important role in DBP formation.

Cleaning and sampling protocol for analysis of mercury and dissolved organic matter in freshwater systems.

Mercury (Hg), and in particular its methylated form (methylmercury, MeHg), is a hazardous substance with the potential to produce significant adverse neurological and other health effects. Enhanced anthropogenic emissions and long-range transport of atmospheric Hg have increased Hg concentrations above background levels in aquatic systems. In this context, the Minamata Convention, a global legally binding agreement that seeks to prevent human exposure to Hg, was signed and enforced by 128 countries, and today more than 90 Parties have ratified it. All these Parties have committed to develop Hg monitoring programs to report the effectiveness of the convention. For this purpose, we provide a standardized cleaning and water sampling protocol for the determination of total-Hg and MeHg in freshwaters at ambient levels. As Hg and organic matter are tightly bound, the protocol also describes sample collection for dissolved organic carbon (DOC) concentration and characterization of dissolved organic matter (DOM) composition by fluorescence spectroscopy. This protocol is highly useful to non-experts without a prior background in Hg sampling and analysis, and can serve as a useful basis for national monitoring programs. Furthermore, this protocol should help increase quantitative inventories of DOC, inorganic-Hg (IHg) and MeHg concentrations and DOM composition in freshwater, which are severely lacking at a global scale. •Provides a standardized method to collect water samples for IHg, MeHg, DOC and DOM composition from freshwater ecosystems.

The interplay between total mercury, methylmercury and dissolved organic matter in fluvial systems: A latitudinal study across Europe.

Large-scale studies are needed to identify the drivers of total mercury (THg) and monomethyl-mercury (MeHg) concentrations in aquatic ecosystems. Studies attempting to link dissolved organic matter (DOM) to levels of THg or MeHg are few and geographically constrained. Additionally, stream and river systems have been understudied as compared to lakes. Hence, the aim of this study was to examine the influence of DOM concentration and composition, morphological descriptors, land uses and water chemistry on THg and MeHg concentrations and the percentage of THg as MeHg (%MeHg) in 29 streams across Europe spanning from 41°N to 64 °N. THg concentrations (0.06-2.78 ng L-1) were highest in streams characterized by DOM with a high terrestrial soil signature and low nutrient content. MeHg concentrations (7.8-159 pg L-1) varied non-systematically across systems. Relationships between DOM bulk characteristics and THg and MeHg suggest that while soil derived DOM inputs control THg concentrations, autochthonous DOM (aquatically produced) and the availability of electron acceptors for Hg methylating microorganisms (e.g. sulfate) drive %MeHg and potentially MeHg concentration. Overall, these results highlight the large spatial variability in THg and MeHg concentrations at the European scale, and underscore the importance of DOM composition on mercury cycling in fluvial systems.

Influence of dissolved organic matter concentration and composition on the removal efficiency of perfluoroalkyl substances (PFASs) during drinking water treatment.

Drinking water treatment plants (DWTPs) are constantly adapting to a host of emerging threats including the removal of micro-pollutants like perfluoroalkyl substances (PFASs), while concurrently considering how background levels of dissolved organic matter (DOM) influences their removal efficiency. Two adsorbents, namely anion exchange (AE) and granulated active carbon (GAC) have shown particular promise for PFAS removal, yet the influence of background levels of DOM remains poorly explored. Here we considered how the removal efficiency of 13 PFASs are influenced by two contrasting types of DOM at four concentrations, using both AE (Purolite A-600®) and GAC (Filtrasorb 400®). We placed emphasis on the pre-equilibrium conditions to gain better mechanistic insight into the dynamics between DOM, PFASs and adsorbents. We found AE to be very effective at removing both PFASs and DOM, while largely remaining resistant to even high levels of background DOM (8 mg carbon L-1) and surprisingly found that smaller PFASs were removed slightly more efficiently than longer chained counterparts, In contrast, PFAS removal efficiency with GAC was highly variable with PFAS chain length, often improving in the presence of DOM, but with variable response based on the type of DOM and PFAS chain length.

Chemodiversity of dissolved organic matter in lakes driven by climate and hydrology.

Despite the small continental coverage of lakes, they are hotspots of carbon cycling, largely due to the processing of terrestrially derived dissolved organic matter (DOM). As DOM is an amalgam of heterogeneous compounds comprising gradients of microbial and physicochemical reactivity, the factors influencing DOM processing at the molecular level and the resulting patterns in DOM composition are not well understood. Here we show, using ultrahigh-resolution mass spectrometry to unambiguously identify 4,032 molecular formulae in 120 lakes across Sweden, that the molecular composition of DOM is shaped by precipitation, water residence time and temperature. Terrestrially derived DOM is selectively lost as residence time increases, with warmer temperatures enhancing the production of nitrogen-containing compounds. Using biodiversity concepts, we show that the molecular diversity of DOM, or chemodiversity, increases with DOM and nutrient concentrations. The observed molecular-level patterns indicate that terrestrially derived DOM will become more prevalent in lakes as climate gets wetter.

Controls of dissolved organic matter quality: evidence from a large-scale boreal lake survey.

Inland waters transport large amounts of dissolved organic matter (DOM) from terrestrial environments to the oceans, but DOM also reacts en route, with substantial water column losses by mineralization and sedimentation. For DOM transformations along the aquatic continuum, lakes play an important role as they retain waters in the landscape allowing for more time to alter DOM. We know DOM losses are significant at the global scale, yet little is known about how the reactivity of DOM varies across landscapes and climates. DOM reactivity is inherently linked to its chemical composition. We used fluorescence spectroscopy to explore DOM quality from 560 lakes distributed across Sweden and encompassed a wide climatic gradient typical of the boreal ecozone. Six fluorescence components were identified using parallel factor analysis (PARAFAC). The intensity and relative abundance of these components were analyzed in relation to lake chemistry, catchment, and climate characteristics. Land cover, particularly the percentage of water in the catchment, was a primary factor explaining variability in PARAFAC components. Likewise, lake water retention time influenced DOM quality. These results suggest that processes occurring in upstream water bodies, in addition to the lake itself, have a dominant influence on DOM quality. PARAFAC components with longer emission wavelengths, or red-shifted components, were most reactive. In contrast, protein-like components were most persistent within lakes. Generalized characteristics of PARAFAC components based on emission wavelength could ease future interpretation of fluorescence spectra. An important secondary influence on DOM quality was mean annual temperature, which ranged between -6.2 and +7.5 °C. These results suggest that DOM reactivity depends more heavily on the duration of time taken to pass through the landscape, rather than temperature. Projected increases in runoff in the boreal region may force lake DOM toward a higher overall amount and proportion of humic-like substances.

Variability in spectral absorbance metrics across boreal lake waters.

Ultraviolet/visible (UV/Vis) absorbance spectroscopy is a commonly used technique for characterizing dissolved organic matter (DOM). We present an analysis of UV/Vis absorbance spectra from 983 lakes throughout Sweden, sampled during autumn 2009. Metrics included both specific absorbances (i.e. absorbance per mass unit of organic carbon), and descriptions of spectral shape. Overall, we found three factors to which all spectral metrics were similarly related: acidity, retention-time, and latitude. In general, alkaline lakes with a long retention time in northern Sweden have lower specific absorbance and steeper spectral slope than acidic lakes with a short retention time in southern Sweden. Relative to the specific absorbance measured at 254 nm (SUVA), commonly used as a measure of DOM aromaticity, the specific absorbance at longer wavelengths and metrics of spectral shape were more sensitive to acidity and less sensitive to latitude. Although different spectral metrics are hypothesized to reflect different properties of DOM, UV/Vis absorbance spectroscopy may not be useful for more refined characterization of organic matter because of the strong inter-correlation between metrics. Nevertheless, it remains useful as a quick, cheap and reliable method of estimating DOM quantity and describing quality. We suggest that the most informative range to measure absorbance is between approximately 250 and 360 nm, where the between-lake variability is largest and absorbance can, in general, be precisely measured.

Selective loss and preservation of lake water dissolved organic matter fluorescence during long-term dark incubations.

The biogeochemical processing of dissolved organic matter (DOM) in inland waters is inherently related to its molecular structure and ecological function. Controlled bioassays are a valuable tool to analyze these relationships, but are seldom conducted and compared at temporal scales that typically prevail in natural inland waters. Here we incubated water from six boreal lakes in the dark and examined changes to the initial fluorescence and absorbance after 3.5 years. We identified five fluorescence components with parallel factor (PARAFAC) analysis (C(C,) C(M), C(A), C(X) and C(T)) and found a consistent change in the relative intensity of two dominant PARAFAC components (increase in C(A):C(C), corresponding to Peak A:Peak C), commonly found in lake water, that represent terrestrially-derived DOM. Surprisingly, we only found minor changes to specific absorbance (SUVA), and did not find any changes to other spectral indexes including the fluorescence index, humification index and freshness index. By incorporating lakes spanning a wide range of initial total organic carbon concentrations (3.7 to 32.5 mg L(-1)), water residence times, and spectral characteristics (e.g. SUVA 1.13 to 3.77 L·mg C(-1)·m(-1)), we found that the relative intensities of two humic-like peaks were the most revealing of changes to DOM structure during dark incubations. We also verified that inner filter effects were adequately corrected within the concentration range of incubated samples. Thus, the processing of DOM under dark conditions, including microbial decomposition and flocculation, may have a greater influence on the humic-like peaks, particularly C(C) (Peak C), with negligible changes to more commonly used spectral indexes.