Effects of Watershed History on Dissolved Organic Matter Characteristics in Headwater Streams

Dissolved organic matter (DOM) is recognized as a major component in the global carbon cycle and is an important driver in aquatic ecosystem function. Climate, land use, and forest cover changes all impact stream DOM and alter biogeochemical cycles in terrestrial environments. We determined the temporal variation in DOM quantity and quality in headwater streams at a reference watershed (REF), a watershed clear-cut 30 years ago (CC), and a watershed converted to a white pine plantation 50 years ago (WP) at the US Forest Service, Coweeta Hydrologic Laboratory, in the Nantahala Mountains of western North Carolina, USA. Average stream dissolved organic carbon (DOC) concentrations in CC or WP were 60 and 80% of those in REF, respectively. Stream DOM composition showed that the difference was mainly due to changes in humic-like components in chromophoric DOM. In addition, excitation–emission matrix fluorescence data with parallel factor analysis indicate that although the concentration of protein-like components did not differ significantly among watersheds, their relative abundance showed an enrichment in CC and WP compared to REF. The ratio of humic acid-type to fulvic acid-type components was highest and lowest at REF and WP, respectively. Our data suggest that forest ecosystem disturbance history affects the DOM quantity and quality in headwater streams over decades as a result of changes in watershed soil organic matter characteristics due to differences in organic matter inputs.     

冰川退缩区不同演替阶段土壤溶解性有机质光谱特征及环境响应

溶解有机质(DOM)作为土壤中最活跃的有机组分,在土壤生物地球化学过程中起着关键作用,探讨植被演替过程中DOM的来源、组成、环境响应与累积规律,对预测土壤碳循环过程具有重要意义。本研究从海螺沟冰川退缩区植被原生演替序列选取演替年龄分别为12、30、40、50、80、120年的样地采集表层和亚表层土壤样本,测定DOM浓度并进行紫外-可见光光谱和三维荧光光谱分析,研究原生演替过程中DOM含量和组成的变化特征及其影响因素。结果表明: 土壤DOM浓度随演替年龄的增加而显著增加。土壤DOM中类蛋白组分、荧光指数和生物指数随演替时间的增加而减小,类腐殖质组分和腐殖化程度随演替过程不断增加,土壤DOM芳香化程度先增加后减小。pH值、铵态氮含量解释了62.2%的表层土壤DOM组分变异,土壤含水率和pH值解释了64.3%的亚表层土壤DOM组分变异,说明环境因素是影响海螺沟冰川退缩区原生演替过程中土壤DOM数量和组成的重要因子。     

Watershed Glacier Coverage Influences Dissolved Organic Matter Biogeochemistry in Coastal Watersheds of Southeast Alaska

The Coast Mountains of southeast Alaska are currently experiencing some of the highest rates of glacier volume loss on Earth, with unknown implications for proglacial stream biogeochemistry. We analyzed streamwater for δ¹⁸O and dissolved organic matter (DOM) biogeochemistry (concentration, δ¹³C-dissolved organic carbon (DOC), and fluorescence characterization) during the 2012 glacial runoff season from three coastal watersheds in southeast Alaska that ranged in glacier coverage from 0 to 49% and a glacier outflow stream. Our goal was to assess how DOM biogeochemistry may change as receding glaciers are replaced by forests and glaciers contribute less meltwater to streamflow. Discharge and streamwater δ¹⁸O varied seasonally reflecting varying contributions of rainfall and snow/icemelt to streamflow over the runoff season. Mean DOC concentrations were lowest in the glacial outflow and highest in the non-glacial stream reflecting an increasing contribution of vascular plant-derived carbon with decreasing watershed glaciation. Fluorescence and δ¹³C-DOC signatures indicated that DOM shifted from vascular plant-derived, humic-like material in the non-glacial stream toward more δ¹³C-DOC enriched, glacier-derived DOM in the glacial outflow. Streamwater δ¹⁸O was significantly correlated to DOC concentration, δ¹³C-DOC, and protein-like fluorescence of streamwater DOM (all P < 0.05), demonstrating that changes in the source of streamwater across the glacial watershed continuum have important implications for the amount and quality of stream DOM export. Overall, our findings show that continued glacial recession and subsequent changes in glacial runoff could substantially influence the biogeochemistry of coastal temperature watersheds by altering the timing, magnitude, and chemical signature of DOM delivered to streams.     

Spatiotemporal Distribution,Sources, and Photobleaching Imprint of Dissolved Organic Matter in the Yangtze Estuary and Its Adjacent Sea Using Fluorescence and Parallel Factor Analysis

To investigate the seasonal and interannual dynamics of dissolved organic matter (DOM) in the Yangtze Estuary, surface and bottom water samples in the Yangtze Estuary and its adjacent sea were collected and characterized using fluorescence excitation-emission matrices (EEMs) and parallel factor analysis (PARAFAC) in both dry and wet seasons in 2012 and 2013. Two protein-like components and three humic-like components were identified. Three humic-like components decreased linearly with increasing salinity (r>0.90, p<0.001), suggesting their distribution could primarily be controlled by physical mixing. By contrast, two protein-like components fell below the theoretical mixing line, largely due to microbial degradation and removal during mixing. Higher concentrations of humic-like components found in 2012 could be attributed to higher freshwater discharge relative to 2013. There was a lack of systematic patterns for three humic-like components between seasons and years, probably due to variations of other factors such as sources and characteristics. Highest concentrations of fluorescent components, observed in estuarine turbidity maximum (ETM) region, could be attributed to sediment resuspension and subsequent release of DOM, supported by higher concentrations of fluorescent components in bottom water than in surface water at two stations where sediments probably resuspended. Meanwhile, photobleaching could be reflected from the changes in the ratios between fluorescence intensity (F_max) of humic-like components and chromophoric DOM (CDOM) absorption coefficient (a355) along the salinity gradient. This study demonstrates the abundance and composition of DOM in estuaries are controlled not only by hydrological conditions, but also by its sources, characteristics and related estuarine biogeochemical processes.     

Distinct Optical Chemistry of Dissolved Organic Matter in Urban Pond Ecosystems

Urbanization has the potential to dramatically alter the biogeochemistry of receiving freshwater ecosystems. We examined the optical chemistry of dissolved organic matter (DOM) in forty-five urban ponds across southern Ontario, Canada to examine whether optical characteristics in these relatively new ecosystems are distinct from other freshwater systems. Dissolved organic carbon (DOC) concentrations ranged from 2 to 16 mg C L^-1 across the ponds with an average value of 5.3 mg C L^-1. Excitation-emission matrix (EEM) spectroscopy and parallel factor analysis (PARAFAC) modelling showed urban pond DOM to be characterized by microbial-like and, less importantly, by terrestrial derived humic-like components. The relatively transparent, non-humic DOM in urban ponds was more similar to that found in open water, lake ecosystems than to rivers or wetlands. After irradiation equivalent to 1.7 days of natural solar radiation, DOC concentrations, on average, decreased by 38% and UV absorbance decreased by 25%. Irradiation decreased the relative abundances of terrestrial humic-like components and increased protein-like aspects of the DOM pool. These findings suggest that high internal production and/or prolonged exposure to sunlight exerts a distinct and significant influence on the chemistry of urban pond DOM, which likely reduces its chemical similarity with upstream sources. These properties of urban pond DOM may alter its biogeochemical role in these relatively novel aquatic ecosystems.     

Effect of Native Vegetation Loss on Stream Ecosystem Processes: Dissolved Organic Matter Composition and Export in Agricultural Landscapes

Stream and river ecosystems are dependent on energetic inputs from their watersheds and thus shifts in land use from forest cover to agriculture will affect stream community composition and function. The disruption of forest-aquatic linkages alters the organic matter resources in agricultural streams. Dissolved organic matter (DOM) is the dominant form of organic matter in aquatic ecosystems, and a microbial energy source that is important for stream respiration. The concentrations and characteristics of DOM are regulated by both terrestrial (for example, terrestrial organic matter supply) and in-stream processes (for example, microbial respiration and periphyton production) that are influenced by land management. The effects of watershed land use and topographic, soil and climatic variables on DOM quantity (dissolved organic carbon concentration and load), source (terrestrial or in-stream) and quality (composition and lability) were measured in 14 streams across an agricultural land-use gradient. DOC concentration was positively correlated with watershed pasture cover and negatively correlated with watershed relief. No watershed variables were important correlates of DOC load. Stream DOM was primarily of terrestrial origin, but DOM in agricultural streams had a greater proportion of sources from in-stream sources. This may be due to reduced connection with riparian vegetation and increased in-stream primary production. We suggest that maintaining watershed tree cover greater than 52% and ensuring less than 10% of the length of riparian corridor is cleared for pasture could minimize changes to DOM composition. This is important to avoid flow-on effects for stream ecosystem processes that are mediated by DOM. Long-term DOM monitoring will be valuable for assessing the functional impacts of land-use change.     

Sources and seasonal patterns of dissolved organic matter (DOM) in the hyporheic zone

The hyporheic zone is a region underneath streambeds that integrates surface and groundwater. Although its location is central to biogeochemical linkages between the riparian zone, dissolved nutrients, and benthic biota, the seasonal quality and likely sources of dissolved organic matter (DOM) in the hyporheic zone are not well understood. To investigate DOM characteristics in the hyporheic zone, water from the surface and subsurface (at depths 20, 60, and 100 cm below the streambed) was sampled every 4 weeks from 2007 to 2008 in a third-order stream in southern Ontario. Using UV spectroscopy, measures of spectral slopes, aromaticity, and A ₂₅₄/A ₃₆₅ ratios (molecular weight) were obtained. Temporal changes in these measures were consistent with watershed processes such as shedding of leaf litter in the fall, and photochemical and biofilm influence in the spring and summer. The fluorescence index (a measure of relative DOM source) suggested that at the surface and in the downwelling zone, DOM microbial sources increased with depth in the sediment, regardless of the season. Excitation–emission matrices (EEMs) showed seasonally distinct, protein-like DOM components of bacterial origin that were stronger in the fall. Leachates from specific allochthonous DOM sources—leaf litter from Betula papyrifera (white birch) and Thuja occidentalis (white cedar)—and an autochthonous source, biofilm, were isolated and incubated with unfiltered surface water. EEMs from these leachates indicated that these sources could indeed help explain observed patterns of DOM in surface and subsurface waters. These results suggest that although DOM sources were relatively constant, biogeochemical processing within the hyporheic zone resulted a DOM pool that was temporally dynamic and altered the nature of organic matter transported downstream into lakes and rivers.     

Fluorescence characteristics and biodegradability of dissolved organic matter in forest and wetland soils from coastal temperate watersheds in southeast Alaska

Understanding how the concentration and chemical quality of dissolved organic matter (DOM) varies in soils is critical because DOM influences an array of biological, chemical, and physical processes. We used PARAFAC modeling of excitation–emission fluorescence spectroscopy, specific UV absorbance (SUVA₂₅₄) and biodegradable dissolved organic carbon (BDOC) incubations to investigate the chemical quality of DOM in soil water collected from 25 cm piezometers in four different wetland and forest soils: bog, forested wetland, fen and upland forest. There were significant differences in soil solution concentrations of dissolved organic C, N, and P, DOC:DON ratios, SUVA₂₅₄ and BDOC among the four soil types. Throughout the sampling period, average DOC concentrations in the four soil types ranged from 9–32 mg C l⁻¹ and between 23–42% of the DOC was biodegradable. Seasonal patterns in dissolved nutrient concentrations and BDOC were observed in the three wetland types suggesting strong biotic controls over DOM concentrations in wetland soils. PARAFAC modeling of excitation–emission fluorescence spectroscopy showed that protein-like fluorescence was positively correlated (r ² = 0.82; P < 0.001) with BDOC for all soil types taken together. This finding indicates that PARAFAC modeling may substantially improve the ability to predict BDOC in natural environments. Coincident measurements of DOM concentrations, BDOC and PARAFAC modeling confirmed that the four soil types contain DOM with distinct chemical properties and have unique fluorescent fingerprints. DOM inputs to streams from the four soil types therefore have the potential to alter stream biogeochemical processes differently by influencing temporal patterns in stream heterotrophic productivity.     

Fluorescence and amino acid characteristics of molecular size fractions of DOM in the waters of Lake Biwa

Dissolved organic matter (DOM) in the waters from Lake Biwa, Japan was fractionated using tangential flow ultrafiltration, and subsequently characterized by fluorescence properties and amino acids. While major dissolved organic carbon (DOC), UV absorbance (Abs), humic-like fluorescence (Flu) and total hydrolyzed amino acids (THAA) occurred in the less than 5 kDa molecular size fraction, they were not evenly distributed among various molecular size fractions. Flu/Abs ratios increased, and THAA/DOC ratios decreased with decreasing molecular size. Humic-like fluorescence occurred in all molecular size fractions, but protein-like fluorescence only occurred in the 0.1 m-GF/F fraction. Subtle differences in amino acid compositions (both individuals and functional groups) were observed between various molecular size fractions, this may indicate the occurrence of DOM degradation from higher to lower molecular weight. The results reported here have significance for further understanding the sources and nature of DOM in aquatic environments.     

Compositional changes and molecular transformations of dissolved organic matter during the arctic spring floods in the lower Churchill watershed (Northern Manitoba,Canada)

The spring flood season in Northern aquatic systems is characterized by rapid changes in river discharge and fluxes of organic and inorganic species, yet remains under sampled. In this study, we examine the molecular characteristics and transformations of dissolved organic matter (DOM) during the Arctic spring season at three locations in the lower Churchill River watershed. Characteristics including dissolved organic carbon concentrations, optical properties (i.e. absorbance and, excitation-emission matrix fluorescence coupled with parallel factor analysis, EEM-PARAFAC) and molecular characterization using high resolution mass spectrometry (HR-MS) were assessed. As spring floods progressed, a significant reduction in DOM spectral slope (S_275–295) and an increase in absorbance (a₂₇₀) were observed suggesting an increase in DOM molecular weight and concentrations at all sampled locations. A maximum in HR-MS lignin-class compounds coincided with peak flow at all sampled locations, further validated with an increase in PARAFAC humic-like components and a minimum in S_275–295. Principal component analyses revealed that both protein and aromatic humic-like material measured by HR-MS and EEM-PARAFAC, respectively, were significantly correlated (ANOVA, p < 0.05), demonstrating similarities in both techniques. Based on network analysis of HR-MS assigned formula, the highest peak flow day was characterized by a maximum in homologous DOM of C₂H₂O and C₂H₄ additions, suggesting structural similarities in newly deposited lignin and humic material. Overall, the progression of the spring freshet shifted the lower Churchill River watershed from an environment rich in proteins and lipids to an aquatic system more abundant in lignin, aromatic and humic DOM.