Regulation of the Nutrient Cycle Pathway and the Microbial Loop Structure by Different Types of Dissolved Organic Matter Decomposition in Lakes

Authors

Lingling Wan, Lu Cao, Chunlei Song, Xiuyun Cao, and Yiyong Zhou

To explore the effect of different types of dissolved organic matter (DOM) decomposition on nutrient cycling pathways and the microbial loop, four lakes with different DOM sources were investigated monthly. In Lake Tangxun, Dolichospermum decay released highly labile dissolved organic nitrogen into the water column. This induced bacterial organic nitrogen decomposition, as indicated by the increased abundance of gltB, gltD, gdh, and glnA as well as aminopeptidase activity. Genes associated with dissimilatory nitrate reduction to ammonium further fueled ammonium accumulation, driving Microcystis blooms in the summer. In Lake Zhiyin, fish bait deposits (high nitrogen, similar to Dolichospermum detritus) also caused Microcystis blooms. Detritus from Microcystis decomposition then produced high levels of labile dissolved organic phosphorus, inducing phosphatase activity and increasing soluble reactive phosphorus concentrations from September to April in Lakes Tangxun and Zhiyin. The high refractory DOM from macrophytes in Lake Houguan led to insufficient nutrient availability, leading to nutrient mutualism between algae and bacteria. The high levels of labile dissolved organic carbon from terrestrial detritus in Lake Yandong increased bacterial biomass and production, resulting in low chlorophyll content due to the competitive relationship between algal and bacterial nutrient requirements. Therefore, different DOM compositions induce unique connections among available nutrients, algae, and bacteria in the microbial loop.

Spatiotemporal analysis of fluorescent dissolved organic matter to identify the impacts of failing sewer infrastructure in urban streams

Authors

Jahir A. Batista-Andrade, Erick Diaz, Diego Iglesias Vega, Ethan Hain, Michael R. Rose, Lee Blaney

Failing sewer infrastructure introduces raw wastewater into streams. We used fluorescence excitation-emission matrix (EEM) spectroscopy and parallel factor analysis (PARAFAC) to track hotspots of raw wastewater in low- and medium-order urban streams that do not receive wastewater effluent but are impacted by sanitary sewer overflows, septic systems, and sewer exfiltration. After analyzing 296 surface water samples from 27 sites in two watersheds over a one-year period, we proposed that the (i) area-normalized ratio of soluble microbial product-like to humic acid-like fluorescence (R4/R5 ≥ 0.85) and (ii) ratio of EEM-PARAFAC components with tryptophan-like and fulvic acid-like fluorescence (C4/C3 ≥ 1.45) could distinguish when and where untreated wastewater is introduced to urban streams. The proposed ratios were validated by co-detection of contaminants of emerging concern, such as sucralose, antibiotics, and UV filters, at concentrations as high as 1354, 108, and 212 ng L⁻¹, respectively. Based on the aggregate data, we identified three sites in rural/suburban areas that were impacted by septic systems and ten sites in urban sections affected by sanitary sewer overflows and/or sewer exfiltration. Moreover, the ratiometric C4/C3 and R4/R5 parameters were immune to dilution effects caused by rain events. Impacts on upstream sites were mostly identified in spring and early summer, but urban hotspots occurred in almost every month. These findings confirmed the potential for EEM-PARAFAC-based wastewater indicators as a quick, easy, cost-effective, and scalable technique to screen for failing sewer infrastructure in low-order streams.

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

Authors

Yongqiang Zhou, Xiaoqin Yu, Lei Zhou, Yunlin Zhang, Hai Xu, Mengyuan Zhu, Guangwei Zhu, Kyoung-Soon Jang, Robert G.M. Spencer, Erik Jeppesen, Justin D. Brookes, Dolly N. Kothawala, Fengchang Wu

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 (S_275-295) 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.

Comparison of organic matter (OM) pools in water, suspended particulate matter, and sediments in eutrophic Lake Taihu, China: Implication for dissolved OM tracking, assessment, and management

Authors

Zhipeng Duan, Xiao Tan, Imran Ali, Xiaoge Wu, Jun Cao, Yangxue Xu, Lin Shi, Wanpeng Gao, Yinlan Ruan, Chen Chen

Suspended particulate matter (SPM) and sediments are important sources of dissolved organic matter (DOM) in lake water. However, studies on what extent and how both sources affect DOM composition are lacking, which hampers DOM management. Herein, DOM, SPM-extracted particulate organic matter (POM), and sediment-extracted organic matter (SOM) were characterized and compared in terms of absorption spectral properties and chemical composition in Lake Taihu, a large cyanobacterial bloom-affected shallow lake. A statistical method was proposed to quantify the similarity of organic matter (OM) in the different states and to evaluate the potential effects of SPM and sediments on DOM. Results showed that POM and DOM were mainly composed of small-molecular-size and low-humified organic components (i.e., 27 %–38 % tryptophan-like and ~30 % protein-like substances), and most of them were derived from autochthonous sources. While tyrosine-like (57 %) and humic-like (27 %) substances were dominant in SOM. The OM similarity between POM and DOM was approximately 1.5 times higher than that between SOM and DOM, indicating the greater effect of SPM than sediments on DOM composition. High pH and low nitrogen (e.g., nitrate and ammonia) were positively correlated to the OM similarity between POM and DOM. Further, the findings indicated that nitrogen limitation enhanced the OM exchange between POM and DOM by promoting the production of extracellular polymeric substances (EPS) in cyanobacterial aggregates. The obtained findings highlighted the importance of SPM in shaping the DOM composition relative to sediments and facilitating the DOM management in bloom-affected lakes.

Molecular-level composition of dissolved organic matter in distinct trophic states in Chinese lakes: Implications for eutrophic lake management and the global carbon cycle

Authors

Shasha Liu, Junwen Hou, Chengyu Suo, Junyi Chen, Xiaohui Liu, Rui Fu, Fengchang Wu

Dissolved organic matter (DOM) is an abundant and mobile part of the aquatic environment and plays important roles in aquatic biogeochemical cycles and the global carbon cycle. Recently, eutrophication has become an important environmental issue in global lakes, but how eutrophication drives changes in the molecular composition of DOM along trophic gradients remains poorly understood. We thus characterized 67 DOM isolates from 11 lakes along a trophic gradient in China by using a combined approach including absorption spectroscopy, excitation-emission matrix fluorescence and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Our results indicated that dissolved organic carbon and absorption coefficients at 350 nm increased with increasing trophic status index. The ultraviolet absorbance at 254 nm and fluorescence intensity of all fluorescent components were higher in eutrophic lakes than in oligotrophic lakes. DOM in high trophic state lakes tended to be dominated by higher molecular weight, unsaturation degree, greater abundance of S-containing compounds, and condensed or polycyclic aromatic compounds than oligotrophic lakes. Additionally, autochthonous DOM characterized by more aliphatic compounds increased with the increasing trophic state. We concluded that nutrient input along with allochthonous DOM favors the lake eutrophication and subsequently increases the release and accumulation of autochthonous DOM. Consequently, eutrophication modifies the structure of the organic matter into more complex materials with increased input of allochthonous DOM and increased release of autochthonous DOM, which could accelerate global carbon cycle processes. Our results here have potential to contribute significantly to future studies of DOM dynamics in eutrophic lakes.

The binding effect and photooxidation on oxytetracycline with algal extracellular polymeric substances and natural organic matter

Authors

Yu Wang, Xinye Gong, Deying Huang, Shuwen Yan, Jibiao Zhang

Surface water contains a large amount of dissolved organic matter (DOM). Interactions between DOM and micropollutants have a significant impact on micropollutant degradation. In this study, algal extracellular polymeric substances (EPS) and natural organic matter (NOM) were selected as two DOM sources and oxytetracycline (OTC) as a representative micropollutant. EPS was mainly composed of tryptophan and protein-like organics, while NOM was mainly composed of fulvic acid-like, humic acid-like, and hydrophobic acid components. In addition, OTC degradation significantly decreased when bound with EPS and the C=O and C–H bonds of CH₂ or CH₃ groups may be involved in binding EPS and OTC, respectively, while –COOH may be involved in the binding of NOM and OTC. Furthermore, triplet intermediates were found to play a major role in OTC photodegradation in both EPS and NOM, with the contribution calculated as 49.96% and 44.61%, respectively. Steady-state concentrations of ³EPS* in EPS and ³NOM* in NOM were 3.59 × 10⁻¹⁴ mol L⁻¹ and 5.54 × 10⁻¹⁵ mol L⁻¹, respectively. These results provide new insights into the degradation of antibiotic-containing wastewater in the natural environment or engineering applications.

Dissolved organic matters with low molecular weight fractions exhibit high photochemical potential for reactive oxygen formation

Authors

Huacheng Xu, Xiaoming Li, Mengjing Guo, Fangfang Li, Keli Yang, Xin Liu

The photochemical properties of dissolved organic matter (DOM) were highly related to the molecular weight (MW) and organic compositions. In this study, the bulk algae- and macrophyte-derived DOM (ADOM and MDOM, respectively) and Suwannee River humic acid (SRHA) were applied and fractionated into low MW- (LMW, <1 kDa) and high MW-(HMW-, 1 kDã0.45 μm) fractions. The formation and mechanisms of photochemically produced reactive intermediates (e.g., HO•, ¹O₂, and ³CDOM*) for these bulk and MW-fractionated samples were compared via the irradiation experiment, fluorescence and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Results showed that humic-/fulvic-like substances were mainly distributed in the LMW fraction which occupied about 44–60% of total organic carbon for ADOM and MDOM and 13% for SRHA. Photochemical experiments showed that the autochthonous DOMs (e.g., ADOM and MDOM) were characterized with comparable formation rates and quantum yields of reactive oxygens with the allochthonous SRHA, suggesting the high photochemical formation potential. Further analysis showed obvious MW-dependent heterogeneities that, irrespective of DOM types, the LMW-fraction exhibited higher formation rates and quantum yields, followed by the bulk- and then the HMW-fractions. The fluorescence and FT-ICR-MS results indicated that the unique biochemical classes, i.e., humic-/fulvic-like moieties and protein-/lipid-derived compounds in the LMW fractions may be responsible for the high apparent quantum yields. This study highlighted the importance of simultaneous characterization of MW and organic compositions for evaluating the photochemical potential and other behaviors and effects of aquatic DOMs.

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

Authors

Most Shirina Begum, Ji-Hyung Park, Liyang Yang, Kyung Hoon Shin, Jin Hur

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.

Fate of trace organic compounds in the hyporheic zone: Influence of microbial metabolism

Authors

Anja Höhne, Birgit M. Müller^, Hanna Schulz, Rebwar Dara, Malte Posselt, Jörg Lewandowski, James L. McCallum

The hyporheic zone (HZ) is considered a hydrodynamically-driven bioreactor with significant pollutant removal capacities and can therefore not only improve wholestream water quality but also preserve human and ecosystem health. Microbial metabolism is hypothesized to play a key role in pollutant transformation in hyporheic sediments of natural streams. However, previous work investigating the influence of microbial metabolism on pollutant transformation has been predominantly laboratory studies. The key challenge for field studies is the appropriate determination of net microbial metabolism, i.e. information on the actual exposure times to specific microbial processes in the investigated system. The present study uses reactive fluorescent tracers to determine microbial metabolism and ultimately its influence on pollutant transformation, e.g. for trace organic compounds, in hyporheic sediments under natural conditions. In particular, the reactive fluorescent tracers resazurin and its main transformation product resorufin were used to determine the microbial metabolism of facultative or obligate aerobes. The influence of the derived microbial metabolism on the transformation of 20 trace organic compounds, such as pharmaceuticals, including 3 parent–daughter pairs, was examined. The present findings validate laboratory results on the microbially-mediated transformation of the anticonvulsant gabapentin to its main transformation product gabapentin lactam under natural conditions. All other TrOCs investigated did not show a clear link between TrOC reactivity to the microbial metabolism informed by the resazurin–resorufin-system. Overall, the present study not only demonstrates the use of the fluorescent tracer-system resazurin and resorufin for determining microbial metabolism of facultative or obligate aerobes but also generally highlights the potential of reactive fluorescent tracers to disentangle specific reactive properties and ultimately their influence on the fate of pollutants in natural HZs.

Changes of DOM and its correlation with internal nutrient release during cyanobacterial growth and decline in Lake Chaohu, China

Authors

Yan Bao, Tao Huang, Chengwu Ning, Tingting Sun, Pengliang Tao, Jie Wang, Qingye Sun

The seasonal changes in dissolved organic matter (DOM), and its correlation with the release of internal nutrients during the annual cycle of cyanobacteria in the eutrophic Lake Chaohu, China, were investigated from four sampling periods between November 2020 and July 2021. The DOM fluorescence components were identified as protein-like C1, microbial humic-like C2, and terrestrial humic-like C3. The highest total fluorescence intensity (F_T) of DOM in sediments during the incubation stage is due to the decomposition and degradation of cyanobacteria remains. The lowest humification of DOM and the highest proportion of C1 in waters during the initial cyanobacterial growth indicate that fresh algae are the main source. The highest molecular weight of DOM and F_T of the C2 in sediments during cyanobacterial outbreaks indicate the concurrent deposition of undegraded cyanobacterial remains and microbial degradation. The components of DOM are affected mainly by the dissolved total phosphorus in waters, while the temperature drives the annual cycle of cyanobacteria. The decreasing C1 in sediments and increasing nutrients in waters from the cyanobacterial incubation to outbreak indicate that mineralization of algal organic matter contributes importantly to the release of internal nutrients, with the strongest release of phosphorus observed during the early growth of cyanobacteria. The humic-like C2 and C3 components could also affect the dynamics of internal phosphorus through the formation of organic colloids and organic–inorganic ligands. The results show that the degradation of DOM leads to nutrients release and thus supports the continuous growth of cyanobacteria in eutrophic Lake Chaohu.