Dissolved Organic Carbon Concentrations Research Articles

Multi-tracer evidence for the presence of autochthonous organic carbon and the role of biological carbon pump in two river–reservoir ecosystems on the Chinese Loess Plateau

The biological carbon pump (BCP) effect of dissolved inorganic carbon (DIC)-enriched karst surface waters is an important carbon sink mechanism that has substantial implications for the study of global missing carbon sinks and carbon cycling. However, the operation of the BCP is not established well in wider inland waters, particularly not in the surface waters of the Chinese Loess Plateau (CLP) that are also DIC-enriched but have high turbidity. In this study, we combined analyses of stable isotopes (δ2H, δ18O, and δ13C) and C/N ratios, ultraviolet absorption spectroscopy, and excitation-emission matrix fluorescence approaches to investigate the sources and compositions of particulate organic carbon (POC) and dissolved organic carbon (DOC) in two river–reservoir ecosystems [the Wulihe (WLH)-river to WLH-reservoir and Honghe (HH)-river to HH-reservoir] on the CLP. Both DOC and POC signals from autochthonous production gradually increased from the river inflow to the reservoir areas along the river flow, particularly during the wet season with the same duration of rain and heat. The WLH-reservoir had higher δ2H, δ18O, and δ13C values, more protein-like fluorescence components, higher chlorophyll-a and DOC concentrations, and lower CO2 efflux than the HH-reservoir. Our results showed that the BCP intensity of the WLH-reservoir was higher than that of the HH-reservoir, probably because of the longer water residence time of the WLH-reservoir. Although the amount of autochthonous dissolved organic matter (Auto-DOM) produced by the BCP in the surface water on the CLP was lower than that in the karst regions of southwest China (CKR), the proportion of Auto-DOM in the CLP was close to that in the CKR, indicating the significance of Auto-DOM in the surface water on the CLP. Furthermore, the BCP-derived Auto-DOM correlated negatively with the partial pressure of CO2, and the WLH-reservoir with a higher BCP effect exhibited CO2 influx in the wet season (−1.47 ± 0.02 g m−2 d−1), indicating that the enhanced BCP process contributed to the water–air interface carbon sink. This study highlighted that enhanced BCP could generate carbon sinks in DIC-enriched but high-turbidity surface waters, providing the underlying theory for extending the BCP carbon sink model to a wider range of surface waters flowing through areas of soil carbonate.

Effect of hydrothermal carbonization aqueous phase on soil dissolved organic matter and microbial community during rice production: A two-year experiment

Hydrothermal carbonization aqueous phase (HAP) containing abundant organic matter (OM) and nutrients (e.g. N and P) are significant in soil nutrients retention capacity and have the potential to return to a paddy field to affect soil microbial diversity and enhance rice yield. In this study, a two-year micro-plot experiment was carried out in a paddy field with the application of cattle manure-derived HAPs prepared at 220 °C and 260 °C (CM220 and CM260) and kitchen waste- (vegetables) derived HAPs prepared at 220 °C and 260 °C (GV220 and GV260). After two-year cultivation, the results showed that soil NH4+-N, dissolved organic carbon (DOC), and available phosphorus (AP) significantly (P < 0.05) increased by 36.4–130.0%, 36.4–130.0%, and 47.8–82.6% but decrease soil pH by 0.43–0.87 units compared with CKU treatment. The HAPs treatments increased baterial richness (Chao 1) but decreased diversity (Shannon). CM260 and GV260 treatments were beneficial for the growth of Actinobacteria but unfavorable to the growth of Proteobacteria. Based on PICRUSt2 results, the abundance of functional genes involved in glucosidase (bglB and malZ), urease (ureC), nitrogen fixation (nifD), denitrification (nirK and nirB), and acid phosphate (phon) slightly increased in HAPs-treated soil and other functional genes were similar in all treatments. Importantly, all the HAP treatments increased the rice yield by 6.7–29.2% compared with the control treatment. The structure equation model (SEM) results demonstrated that soil NH4+-N (λ = 0.35) and DOC content (λ = 0.70) were the main driving factors of higher rice yield (P < 0.05). GV220 and GV260 treatments remarkably enhanced the grain N content by 6.5% compared with the control treatment (P < 0.05). These findings indicated that returning HAPs into paddy soil would not negatively affect soil health and improve soil structure and fertility. Overall, this study provides a new disposal way of green organic wastewater and emphasize the importance of microbial structure and composition for paddy field.

Increasing riverine export of dissolved organic carbon from China.

River transport of dissolved organic carbon (DOC) to the ocean is a crucial but poorly quantified regional carbon cycle component. Large uncertainties remaining on the riverine DOC export from China, as well as its trend and drivers of change, have challenged the reconciliation between atmosphere-based and land-based estimates of China's land carbon sink. Here, we harmonized a large database of riverine in-situ measurements and applied a random forest model, to quantify riverine DOC fluxes (FDOC ) and DOC concentrations (CDOC ) in rivers across China. This study proposes the first DOC modeling effort capable of reproducing well the magnitude of riverine CDOC and FDOC , as well as its trends, on a monthly scale and with a much wider spatial distribution over China compared to previous studies that mainly focused on annual-scale estimates and large rivers. Results show that over the period 2001-2015, the average CDOC was 2.25 ± 0.45 mg/L and average FDOC was 4.04 ± 1.02 Tg/year. Simultaneously, we found a significant increase in FDOC (+0.044 Tg/year2 , p = .01), but little change in CDOC (-0.001 mg/L/year, p > .10). Although the trend in CDOC is not significant at the country scale, it is significantly increasing in the Yangtze River Basin and Huaihe River Basin (0.005 and 0.013 mg/L/year, p < .05) while significantly decreasing in the Yellow River Basin and Southwest Rivers Basin (-0.043 and -0.014 mg/L/year, p = .01). Changes in hydrology, play a stronger role than direct impacts of anthropogenic activities in determining the spatio-temporal variability of FDOC and CDOC across China. However, and in contrast with other basins, the significant increase in CDOC in the Yangtze River Basin and Huaihe River Basin is attributable to direct anthropogenic activities. Given the dominance of hydrology in driving FDOC , the increase in FDOC is likely to continue under the projected increase in river discharge over China resulting from a future wetter climate.

Self‐diagnosis of model suitability for continuous measurements of stream‐dissolved organic carbon derived from in situ UV–visible spectroscopy

AbstractApplication of high‐frequency monitoring of dissolved organic carbon (DOC) is difficult in instances where training datasets are challenging to develop (e.g., remote locations) and the relationship between optical features and DOC concentration changes due to environmental or landscape shifts (e.g., climate or land‐use change). We developed and compared three partial least squares (PLS) models using in situ water level measurements, conductivity, and UV–Vis spectral attenuation to predict DOC. Two site‐specific models were developed using data from a hillslope‐dominated forest or a low‐relief wetland‐pond‐dominated stream catchment. The third model, using data from both sites, exhibited the best performance (DOC range = 4–15.5 mg C L−1, mean = 8.38 mg C L−1, training RMSE = 0.34 mg C L−1, internal validation RMSE = 0.50 mg C L−1, external validation RMSE = 2.43 mg C L−1). We further demonstrate using PLS model statistics to monitor performance and elucidate when and how models should be updated. These statistics, Hotelling's T2 and squared prediction errors, are useful consistency checks for the predictions made and detect underlying inconsistencies that, if undetected, can reduce the robustness of DOC prediction. For example, via the T2 statistic, we identified the summer–autumn transition as a period when DOC composition differed from what was represented in the training dataset. We also determined that elevated SUVA254 values contributed to the overall bias observed in predictions made during the subsequent year as part of the external validation. This enabled the application of a bias correction that reduced the RMSE from 2.43 to 0.89 mg C L−1. The method presented here could be applied to future monitoring programs enabling model updates to monitor DOC fluxes accurately from optical datasets (e.g., attenuance or fluorescence) in the face of developing datasets in remote locations or environmental change. Implementation of this approach may also identify possible regime shifts or landscape and hydrologic change associated with climate and other environmental changes relevant to terrestrial to aquatic fluxes.

Effect of Electrochemical Pre-Oxidation for Mitigating Ultrafiltration Membrane Fouling Caused by Extracellular Organic Matter

Algal extracellular organic matter (EOM) will cause grievous membrane fouling during the filtration of algae-laden water; hence, boron-doped diamond (BDD) anodizing was selected as the pretreatment process before the ultrafiltration, and the EOM fouling mitigation mechanism and the purification efficiency were systematically investigated. The results showed that BDD oxidation could significantly alleviate the decline of membrane flux and reduce membrane fouling, and the effect was more notable with an increase in oxidation time. Less than 10% flux loss happened when oxidation duration was 100 min. The dominant fouling model was gradually replaced by standard blocking. BDD anodizing preferentially oxidizes hydrophobic organic matter and significantly reduces the DOC concentration in EOM. The effluent DOC was reduced to less than 1 mg/L when 100 min of BDD anodizing was applied. After the pre-oxidation of BDD, the zeta potential and interfacial free energy, including the cohesive and adhesive free energy, were all constantly increasing, which implied that the pollutants would agglomerate and deposit, and the repulsion between foulants and the ultrafiltration membrane was augmented with the extensive oxidation time. This further confirms the control of BDD on membrane fouling. In addition, the BDD anodizing coupled ultrafiltration process also showed excellent performance in removing disinfection by-product precursors.

Variations in the archaeal community and associated methanogenesis in peat profiles of three typical peatland types in China

BackgroundPeatlands contain about 500 Pg of carbon worldwide and play a dual role as both a carbon sink and an important methane (CH4) source, thereby potentially influencing climate change. However, systematic studies on peat properties, microorganisms, methanogenesis, and their interrelations in peatlands remain limited, especially in China. Therefore, the present study aims to investigate the physicochemical properties, archaeal community, and predominant methanogenesis pathways in three typical peatlands in China, namely Hani (H), Taishanmiao (T), and Ruokeba (R) peatlands, and quantitively determine their CH4 production potentials.ResultsThese peatlands exhibited high water content (WC) and total carbon content (TC), as well as low pH values. In addition, R exhibited a lower dissolved organic carbon concentration (DOC), as well as higher total iron content (TFe) and pH values compared to those observed in T. There were also clear differences in the archaeal community between the three peatlands, especially in the deep peat layers. The average relative abundance of the total methanogens ranged from 10 to 12%, of which Methanosarcinales and Methanomicrobiales were the most abundant in peat samples (8%). In contrast, Methanobacteriales were mainly distributed in the upper peat layer (0–40 cm). Besides methanogens, Marine Benthic Group D/Deep-Sea Hydrothermal Vent Euryarchaeotic Group 1 (MBG–D/DHVEG–1), Nitrosotaleales, and several other orders of Bathyarchaeota also exhibited high relative abundances, especially in T. This finding might be due to the unique geological conditions, suggesting high archaeal diversity in peatlands. In addition, the highest and lowest CH4 production potentials were 2.38 and 0.22 μg g−1 d−1 in H and R, respectively. The distributions of the dominant methanogens were consistent with the respective methanogenesis pathways in the three peatlands. The pH, DOC, and WC were strongly correlated with CH4 production potentials. However, no relationship was found between CH4 production potential and methanogens, suggesting that CH4 production in peatlands may not be controlled by the relative abundance of methanogens.ConclusionsThe results of the present study provide further insights into CH4 production in peatlands in China, highlighting the importance of the archaeal community and peat physicochemical properties for studies on methanogenesis in distinct types of peatlands.

Leaching is the main pathway of nitrogen loss from a citrus orchard in Central China

Due to the high application rates and low utilization efficiency of inorganic nitrogen (N) fertilizer, conventional citrus orchards tend to cause N losses and extensive pollution. In order to address these issues, it is essential to identify the leading cause of N loss by citrus orchard N mass balance. In the present study, a two-year field experiment was performed on 4 different treatments (CK: no N fertilizer; CF: conventional N fertilizer; NR: 70% of conventional N fertilizer; OM: NR with organic manure) to quantify the pathways of N loss in citrus orchards in Hubei Province, China. Our findings revealed that leaching (17.0%) was the dominant N loss pathway in the conventional citrus orchard of central China, followed by runoff (2.9%), NH3 volatilization (2.3%), and N2O emission (0.5%). Reduced N fertilizer rates (−30.0%) led to a significant reduction in gaseous N loss (−34.9%), runoff N loss (−20.3%), and N leaching (−13.0%) via the reduced content of soil NH4+ and soil NO3-. Interestingly, the presence of organic manure reduced 15.2% of runoff N loss, 3.8% of N leaching and 6.9% of total N loss via reduced soil NO3-, but increased 39.6% of gaseous N loss via increased soil DOC. On the other hand, the low N fertilizer rates suppressed N uptake of citrus by reducing the content of soil NO3-, while organic manure promoted N uptake of citrus via the increased content of soil DOC. Overall, using organic manure as a substitute provides a better solution to fertilization for the citrus orchards in central China compared to reducing N fertilizer rates.

Spatio-temporal variations in organic carbon composition driven by two different major phytoplankton communities in the Ross Sea, Antarctica

The compositions of organic carbon could be important in determining biological carbon pump efficiency. However, little information on them in relation to each algal assemblage is currently available in the Ross Sea. Here, we investigated the seasonal variations in organic carbon composition and the relative abundance of each organic carbon, including particulate organic carbon (POC), dissolved organic carbon (DOC), and transparent exopolymer particles (TEPs), characterized by different algal groups in the Ross Sea. The average POC and DOC contributions to the total organic carbon (TOC = POC + DOC) were 13.8 ± 3.7 % and 86.2 ± 3.7 % in mid-January 2019 and 20.9 ± 4.1 % and 79.1 ± 4.1 % in February–March 2018, respectively. The carbon content of TEP (TEP-C) contributed 19.6 ± 11.7 % and 4.6 ± 7.0 % of POC and TOC in mid-January and 36.2 ± 14.8 % and 9.0 ± 6.7 % in February–March, respectively. We found that the organic carbon compositions were affected by seasonal variations in the phytoplankton bloom phase, physical characteristics, and phytoplankton community structure. DOC concentrations and contributions to the TOC increased as phytoplankton cells became senescent in mid-January and decreased in February–March when phytoplankton were relatively active. From February–March, the deepened mixed layer depth encouraged TEP formation, subsequently increasing the TEP contributions. Regardless of the sampling season, all organic carbon concentrations per unit Chl-a were significantly higher in P. antarctica–abundant groups. The DOC contributions to the TOC were correspondingly higher at the P. antarctica–abundant stations in mid-January, which indicates that P. antarctica could be also important in the DOC contributions in the Ross Sea. The rapid alteration in environmental characteristics and phytoplankton community structures in the Ross Sea due to climate change could affect the organic carbon pool at the euphotic layer which consequently could determine the efficiency of the biological pump.

Pyrolysis temperature dependent effects of biochar on shifting fluorescence spectrum characteristics of soil dissolved organic matter under warming

Biochar generally shift the content and molecular composition of soil dissolved organic matter (DOM) which represent the reactive components and have essential roles in coupling elemental cycling in soil. However, it is not clear how the effects of biochar on soil DOM composition is shifted under warming. This causes a knowledge gap to fully understand the fate of SOM affected by biochar application in a warming climate. To fill this gap, we conducted a simulated climate warming incubation of soil to study the influence of biochar with different pyrolysis temperatures and feedstock types on soil DOM components composition. Three-dimensional fluorescence spectrum analysis combining excitation emission matrix-parallel factor analysis (EEM-PARAFAC), fluorescence region integral (FRI), UV–vis spectrometry, principal component analysis (PCA), clustering analysis, Pearson correlation and multi-factor analysis of variance on fluorescence parameters (including FRI on Region I-V, FI, HIX, BIX, H/P) and soil DOC and DON content were analyzed for this purpose. Results showed that biochar shifted soil DOM composition and enhanced soil humification, which was dominantly pyrolysis-temperature dependent. Biochar shifted the soil DOM components composition probably through mediating soil microbial processing rather than direct input of their pristine DOM, and the influence of biochar on soil microbial processing was pyrolysis-temperature dependent and highly affected by warming. Medium-temperature biochar was more efficient for enhancing soil humification, by accelerating the transformation of protein-like components into humic-like components. Soil DOM composition presented a rapid response to warming, and long-term incubation may eliminate the effects of warming on shifting soil DOM composition. By revealing the heterogeneous effects of biochar with different pyrolysis temperatures on fluorescence characteristics of soil DOM components, our study provides a hint for the essential role of biochar on enhancing soil humification, and also suggests a vulnerability of biochar for soil carbon sequestration under warming.

FT-ICR-MS combined with fluorescent spectroscopy reveals the driving mechanism of the spatial variation in molecular composition of DOM in 22 plateau lakes

Dissolved organic matter (DOM) is the largest carbon pool and directly affects the biogeochemistry in lakes. In the current study, fourier transform ion cyclotron mass spectrometry (FT-ICR-MS) combined with fluorescent spectroscopy was used to assess the molecular composition and driving mechanism of DOM in 22 plateau lakes in Mongolia Plateau Lakes Region (MLR), Qinghai Plateau Lakes Region (QLR) and Tibet Plateau Lakes Region (TLR) of China. The limnic dissolved organic carbon (DOC) content ranged from 3.93 to 280.8 mg L−1 and the values in MLR and TLR were significantly higher than that in QLR. The content of lignin was the highest in each lake and showed a gradually decreasing trend from MLR to TLR. Random forest model and structural equation model implied that altitude played an important role in lignin degradation while the contents of total nitrogen (TN) and chlorophyll a (Chl-a) have a great influence on the increase of DOM Shannon index. Our results also suggested that the inspissation of DOC and the promoted endogenous DOM production caused by the inspissation of nutrient resulted in a positive relationship between limnic DOC content and limnic factors such as salinity, alkalinity and nutrient concentration. From MLR to QLR and TLR, the molecular weight and the number of double bonds gradually decreased but the humification index (HIX) also decreased. In addition, from the MLR to the TLR, the proportion of lignin gradually decreased, while the proportion of lipid gradually increased. Both above results suggested that photodegradation was dominated in lakes of TLR, while microbial degradation was dominated in lakes of MLR.

Depth Moderates DOC Impact on Cold‐Water Refugia in Small, Northern Temperate Lakes

AbstractWidespread changes in dissolved organic carbon (DOC) concentrations in lakes of the Northern Hemisphere are well documented, and there is a need to understand the ecological implications for changes in cold‐water refugia. DOC controls thermal structure in small, wind‐sheltered lakes, thus influencing the volume and persistence of the hypolimnion and cold‐water habitat. We explored the relationship between the quantity and quality of DOC and the availability of cold‐water habitat over the course of summer stratification in small lakes of varying depths. The ratio of the hypolimnetic volume to total lake volume was calculated to assess the relative changes in cold‐water habitat availability in each lake over time. DOC concentration, maximum lake depth, and the interaction between DOC concentration and maximum lake depth explained 87% of the variability in percent change in hypolimnion volume ratio across studied lakes. Hypolimnion compression was greater in shallow, low DOC lakes, whereas deeper, intermediate DOC lakes had more persistent hypolimnion volumes over the course of summer stratification. These results demonstrate that depth moderates the effect of DOC on the volume and persistence of cold‐water refugia availability in north temperate lakes, advancing our understanding of differing lake sensitivity in a rapidly changing physical and chemical environment.

Hyporheic exchange in an urban beaver pond mediates high nutrient groundwater inflow and pond productivity

The rebound of beaver populations across North America has resulted in new understanding of how their alteration of stream channels affects hydrology and biogeochemical cycling, but their increased impact on urban areas has not been well investigated. Urban beaver ponds have the potential to slow and retain runoff, reconnect surrounding floodplains, and reduce nutrients. Where management allows, beaver ponds may partially ameliorate water quality problems in urban streams and enhance the ecological function of the broader riparian zone. In this study we measured water chemistry in surface (over ten months) and hyporheic (over three months) waters, including nitrate, ammonium, and dissolved organic carbon (DOC), to assess the impact of urban beaver dams on water quality. Pond water is sourced from groundwater, with anoxic conditions in the surface water at the top of the pond that become increasingly oxic moving longitudinally through the pond. Large diel dissolved oxygen swings in the pond indicate high sestonic productivity. There are distinct hyporheic geochemical signatures above and below the dam as well as across the dam indicating the dam is driving downwelling above the dam and upwelling below. Hyporheic ammonium concentrations and surface nitrate concentrations are high above the dam and decrease below the dam, showing that shifting oxic conditions drive nitrogen speciation. The δ15N and δ18O values of nitrate point to diffuse sewage leaks as the main source of nutrients to the pond instead of overland runoff. In addition, surface waters have lower δ15N and δ18O of nitrate and DOC concentrations than groundwaters, indicating denitrification may drive the decrease in nitrate concentration. With increasing presence of beaver in urban streams, surface water-groundwater interactions through urban beaver dams have the potential to remediate urban sources of nutrients from ponds.

Factors affecting broadscale variation in nearshore water-column organic carbon concentrations along the Great Barrier Reef

Organic carbon is a key energy source in marine food-webs, but elevated concentrations can have negative ecological impacts. We used 12 years of marine physiochemical, climate, and near-surface sea and meteorological condition data to investigate broadscale correlates and potential drivers of variability in dissolved and particulate organic carbon (DOC and POC, respectively) concentrations in coastal waters of the Great Barrier Reef (GBR), Australia. DOC concentrations were higher when salinity was lower, when the Southern Oscillation Index was more positive, and at times of greater northward wind speeds. POC concentrations were higher in shallower waters and were positively correlated with total suspended solids and chlorophyll a concentrations. Latitude was important for structuring variation in organic carbon concentrations, likely reflecting terrestrial material from rivers and broader marine processes. We conclude that variability in broadscale patterns of DOC concentrations in GBR coastal waters is likely most sensitive to material discharge from rivers as well as oceanographic and climatic processes and forcing. Variability in broadscale patterns of POC concentrations in coastal waters of the GBR is likely most affected by sediment resuspension and phytoplankton biomass accumulation.

Effects of simulated acid rain and carbon-rich water on mercury mobilization in soils amended with aluminum-based drinking water treatment residuals

Mercury (Hg) contamination in soils is of concern because of its known adverse effects on ecosystem functions and human health. Research on how to reduce Hg contamination in soil is still needed, mainly because of the difficulties in remediating Hg-contaminated soils while minimizing adverse effects on treated systems. We investigated the potential of a waste substrate, aluminum (Al)-based drinking water treatment residuals (Al-WTRs), as a low-cost sorbent for immobilizing the mobile fraction of Hg in contaminated soils using column leaching studies. Because of the known role of acidic deposition and dissolved organic matter on the environmental cycling of Hg, columns packed with Hg-contaminated alluvial soils collected from the watershed of Poplar Creek in Tennessee of USA were leached using either the synthetic precipitation leaching procedure (SPLP) to simulate the effects of acid rain or low pH dissolved organic carbon (DOC) rich river water (Suwannee River water, pH 4.20) to mimic soil flooding events with DOC-rich waters. The results show that, for soils with very high mobile Hg fractions, control columns without Al-WTR leached with the SPLP solution retained only 51% of total-Hg, which was significantly less (p ​< ​0.05) than in the Al-WTR treated soil columns (up to 80%). Leaching with DOC-rich river water (53.3 ​mg ​C/L) decreased the sorption capacity of Al-WTR. Using waters with increasing DOC concentrations (from 5.33 to 40 ​mg ​C/L) resulted in the removal of 63% of the initial mass of Hg in the control columns compared to 22–29% in the columns amended with 2 and 5% Al-WTR. Overall, Al-WTR can immobilize Hg under extreme leachability conditions and should be considered as a potential sorbent for in situ remediation of Hg-contaminated soils. However, further studies are needed on the fate of Al-WTR-immobilized Hg.

Dissolved organic carbon export in a small, disturbed peat catchment: Insights from long‐term, high‐resolution, sensor‐based monitoring

AbstractUnderstanding dissolved organic carbon (DOC) export dynamics from carbon‐rich environments is critical. Peatlands act as terrestrial carbon stores, and consequently supply substantial amounts of DOC to drainage. This DOC flux is temporally heterogeneous and subject to long‐ and short‐term variability. Ultrahigh temporal resolution sampling (&lt; hourly) is still in‐frequent in peatland catchments. We used a field‐deployable —ultraviolet–visible light spectrometer (Spectro::lyser™) and monitored DOC flux from a temperate peatland over 31 months to examine seasonal and event dynamics. DOC concentration varied from 6.8 to 63.5 mg L−1, in the higher reported range for peatlands and showed clear seasonal (high‐summer, low‐winter) variability coinciding with elevated biological productivity in the peatland. Discharge was an unreliable predictor of instantaneous DOC concentration overall, with antecedent water temperatures proving the most reliable predictor overall. Discharge drove total DOC export in the catchment, where the top 10% of flow events, accounted for 41.3% of all DOC exported—increasing to 84.6% in the top 50% of flow events. Total estimated catchment DOC flux was sensitive to measurement frequency: increasing from every 30 min to daily altered export estimates by &lt; 1%, increasing to &gt; 10% at 1‐week intervals. The variation in estimated flux increased approximately linearly with reduced sampling frequency, reaching &gt; 40% at monthly intervals. High‐resolution data reveal the large amount of within‐site complexity of DOC export dynamics in a temperate peatland and provide evidence on the subsequently recommended sampling frequency for the future elucidation of detailed DOC budgets in these environments.

Algal organic matter impact on 2-methylisopropanol and geosmin adsorption by activated carbon: Variation with algae growth and decay, prediction by fluorescence surrogates

Algae-producing odorants have negative effects on the aesthetic quality of drinking water, and activated carbon adsorption is commonly used to abate the odorants. However, in eutrophic waters, algal organic matter (AOM) produced by the dominant cyanobacteria (e.g., Microcystis aeruginosa) strongly interferes with the activated carbon adsorption of trace odorants from source waters. In this study, the applicability of using spectrometric surrogates to evaluate the effect of AOM from Microcystis aeruginosa on odorant adsorption by activated carbon was investigated. During the stationary phase, the DOC concentration of extracellular organic matter (EOM) increased due to algal metabolism (from 3.52 mg/L to 7.81 mg/L) and further accumulated (to 12.40 mg/L) during the decline phase due to the release of intracellular organic matter (IOM), resulting in increased competition against odorants. The adsorption of chromogenic organics in AOM was first evaluated to screen possible spectrometric surrogates for predicting odorant adsorption. The fluorescence component (Ex: 260 nm/Em: 400–460 nm) was the best candidate for predicting odorant adsorption in both AOM solutions and reservoir water. In contrast, poor performance was found for the commonly used UV absorbance at 254 nm and protein-like fluorescence components, due to the weak adsorbability of corresponding chromogenic materials. Our results indicate that fluorescence spectroscopy is promising in predicting odorant adsorption with AOM interference in source waters.

Water-soluble organic carbon release from mineral soils and sediments in an irrigated agricultural system

Water interactions with soil and vegetation are greatly altered in agricultural watersheds compared to natural landscapes, which impacts sources and fates of organic carbon (OC). While mineral soil horizons in natural ecosystems primarily act as filters for dissolved organic carbon (DOC) leached from organic surface horizons, tilled soils largely lack an organic horizon and their mineral horizons therefore act as a source for both DOC and sediment to surface waters. Irrigated watersheds highlight this difference, as DOC and total suspended sediment (TSS) concentrations simultaneously increase during the low-discharge irrigation season, suggesting that sediment-associated OC may constitute a significant source of DOC. While water-soluble OC (WSOC) from sediments and soils has been found to be compositionally similar to stream DOC, these contributions remain poorly quantified in agricultural streams. To address this, we conducted abiotic solubilization experiments using sediments (suspended and bed) and soils from an irrigated agricultural watershed in northern California, USA. Sediments (R2 > 0.99) and soils (0.74 < R2 < 0.89) displayed linear solubilization behaviors over the range of concentrations tested. Suspended sediment from the irrigation season exhibited the largest solubilization efficiency (10.9 ± 1.6% TOCsediment solubilized) and potential (1.79 ± 0.26 mg WSOC g−1 dry sediment), followed by suspended sediment from a winter storm, then bed sediment and soils. Successive solubilization experiments increased the total release of WSOC by ∼50%, but most (88–97%) of the solid-phase OC remained insoluble in water. Using these solubilization potential estimates and measured TSS concentrations, we estimated that WSOC from suspended sediment in streams represented 4–7% of the annual DOC export from the watershed. However, field sediment export is much higher than what is represented by suspended sediment in the water column, therefore field-scale contributions from sediments could be much higher than estimated.

Artificial neural network implementation for dissolved organic carbon quantification using fluorescence intensity as a predictor in wastewater treatment plants

Although spectroscopic methods provide a fast and cost-effective means of monitoring dissolved organic carbon (DOC) in natural and engineered water systems, the prediction accuracy of these methods is limited by the complex relationship between optical properties and DOC concentration. In this study, we developed DOC prediction models using multiple linear/log-linear regression and feedforward artificial neural network (ANN) and investigated the effectiveness of spectroscopic properties, such as fluorescence intensity and UV absorption at 254 nm (UV254), as predictors. Optimum predictors were identified based on correlation analysis to construct models using single and multiple predictors. We compared the peak-picking and parallel factor analysis (PARAFAC) methods for selecting appropriate fluorescence wavelengths. Both methods had similar prediction capability (p-values >0.05), suggesting PARAFAC was not necessary for choosing fluorescence predictors. Fluorescence peak T was identified as a more accurate predictor than UV254. Combining UV254 and multiple fluorescence peak intensities as predictors further improved the prediction capability of the models. The ANN models outperformed the linear/log-linear regression models with multiple predictors, achieving higher prediction accuracy (peak-picking: R2 = 0.8978, RMSE = 0.3105 mg/L; PARAFAC: R2 = 0.9079, RMSE = 0.2989 mg/L). These findings suggest the potential to develop a real-time DOC concentration sensor based on optical properties using an ANN for signal processing.

Canopy Phenology and Meteorology Shape the Seasonal Dynamics in Hydrological Fluxes of Dissolved Organic Carbon in an Evergreen Broadleaved Subtropical Forest in Central Japan

Seasonal variabilities in hydrological fluxes of dissolved organic carbon (DOC) and their driving factors in the evergreen broad-leaved forest are inadequately understood. To aid this understanding, we conducted a three-year study to examine seasonal changes in DOC concentration and flux in throughfall, stemflow, and litter leachate in an evergreen broad-leaved subtropical forest in central Japan. We specifically addressed (1) how DOC in different hydrological fluxes vary on a monthly to seasonal basis, and (2) how canopy phenology and meteorology shape the DOC concentration and flux of throughfall, stemflow, and litter leachate trends in this evergreen forest. Clear seasonal changes were found in throughfall and stemflow DOC concentration but not in litter leachate DOC concentration; the highest throughfall DOC concentrations were observed in spring (10.03 mg L−1 in 2017 and 9.59 mg L−1 in 2018, respectively) and the highest stemflow DOC concentrations were observed in summer (13.95 mg L−1 in 2017 and 16.50 mg L−1 in 2018, respectively). Correlation analysis revealed the monthly throughfall DOC concentration to be positively related to the dry weight of fallen leaves (r = 0.72, p &lt; 0.05) and flowers (r = 0.91, p &lt; 0.05). In addition, Random Forest models predicted that the dry weight of flowers was a primary driver of throughfall DOC concentration and that the DOC concentrations of stemflow and litter leachate were constrained by the throughfall DOC concentration. DOC fluxes in different hydrological flux were significantly positive related to bulk precipitation amounts and temperature. Moreover, the throughfall DOC concentration had a considerable effect on throughfall and litter leachate DOC fluxes. Over 75% of annual net tree-DOC (throughfall + stemflow) fluxes and more than 70% of the annual litter leachate DOC fluxes were produced in the flowering season. Thus, we speculated that the seasonal phenological canopy changes (leaf emergence, fallen leaves, flowering, and pollen) and the sufficient rainfall had great impacts on the amount and quality of DOC concentrations in the evergreen forest; and, furthermore, that the DOC from different forest hydrological fluxes was a significant fraction of the carbon that accumulates in soils.

Effects of dissolved organic matter derived from cow manure on heavy metal(loid)s and bacterial community dynamics in mercury-thallium mining waste slag.

Organic amendments in aided phytostabilization of waste slag containing high levels of heavy metal (loid)s (HMs) are an important way to control the release of HMs in situ. However, the effects of dissolved organic matter (DOM) derived from organic amendments on HMs and microbial community dynamics in waste slag are still unclear. Here, the effect of DOM derived from organic amendments (cow manure) on the geochemical behaviour of HMs and the bacterial community dynamics in mercury (Hg)-thallium (Tl) mining waste slag were investigated. The results showed that the Hg-Tl mining waste slag without the addition of DOM continuously decreased the pH and increased the EC, Eh, SO42-, Hg, and Tl levels in the leachate with increasing incubation time. The addition of DOM significantly increased the pH, EC, SO42-, and arsenic (As) levels but decreased the Eh, Hg, and Tl levels. The addition of DOM significantly increased the diversity and richness of the bacterial community. The dominant bacterial phyla (Proteobacteria, Firmicutes, Acidobacteriota, Actinobacteriota, and Bacteroidota) and genera (Bacillus, Acinetobacter, Delftia, Sphingomonas, and Enterobacter) were changed in association with increases in DOM content and incubation time. The DOM components in the leachate were humic-like substances (C1 and C2), and the DOC content and maximum fluorescence intensity (FMax) values of C1 and C2 in the leachate decreased and first increased and then decreased with increasing incubation time. The correlations between HMs and DOM and the bacterial community showed that the geochemical behaviours of HMs in Hg-Tl mining waste slag were directly influenced by DOM-mediated properties and indirectly influenced by DOM regulation of bacterial community changes. Overall, these results indicated that DOM properties associated with bacterial community changes increased As mobilization but decreased Hg and Tl mobilization from Hg-Tl mining waste slag.