How humans alter dissolved organic matter composition in freshwater: relevance for the Earth’s biogeochemistry

Dissolved organic matter (DOM) is recognized for its importance in freshwater ecosystems, but historical reliance on DOM quantity rather than indicators of DOM composition has led to an incomplete understanding of DOM and an underestimation of its role and importance in biogeochemical processes. A single sample of DOM can be composed of tens of thousands of distinct molecules. Each of these unique DOM molecules has their own chemical properties and reactivity or role in the environment. Human activities can modify DOM composition and recent research has uncovered distinct DOM pools laced with human markers and footprints. Here we review how land use change, climate change, nutrient pollution, browning, wildfires, and dams can change DOM composition which in turn will affect internal processing of freshwater DOM. We then describe how human-modified DOM can affect biogeochemical processes. Drought, wildfires, cultivated land use, eutrophication, climate change driven permafrost thaw, and other human stressors can shift the composition of DOM in freshwater ecosystems increasing the relative contribution of microbial-like and aliphatic components. In contrast, increases in precipitation may shift DOM towards more relatively humic-rich, allochthonous forms of DOM. These shifts in DOM pools will likely have highly contrasting effects on carbon outgassing and burial, nutrient cycles, ecosystem metabolism, metal toxicity, and the treatments needed to produce clean drinking water. A deeper understanding of the links between the chemical properties of DOM and biogeochemical dynamics can help to address important future environmental issues, such as the transfer of organic contaminants through food webs, alterations to nitrogen cycling, impacts on drinking water quality, and biogeochemical effects of global climate change.

     

Photooxidation of wetland and riverine dissolved organic matter: altered copper complexation and organic composition

In natural waters, the uptake of transition metals such as copper (Cu) by aquatic biota depends on the activity of the free cupric ion ({Cu²⁺}) rather than on total Cu concentration. Thus, an important ecological function of dissolved organic matter (DOM) in aquatic ecosystems is Cu–DOM complexation, which greatly decreases the {Cu²⁺}. However, Cu bioavailability is greatly modified by source and environmental history of DOM because DOM affinity for Cu varies by orders of magnitude among DOM sources; moreover, DOM is photochemically unstable. During 72-h irradiation experiments at intensities approximating sunlight with DOM from a palustrine wetland and a third-order river, we investigated photooxidative effects on DOM complexation of Cu as well as spectral and chemical changes in DOM that might explain altered Cu complexation. Irradiation decreased Cu complexation by riverine DOM, but unexpectedly increased Cu complexation by wetland DOM, resulting in 150% greater {Cu²⁺} in riverine DOM at the same dissolved organic carbon concentrations. The specific ultraviolet absorption (SUVa) and humic substances tracked photochemical changes in the conditional stability constants of Cu–DOM complexes, suggesting that the aromaticity of DOM influences its affinity for Cu. Carbonyl concentration in ¹³C nuclear magnetic resonance spectra (¹³C-NMR) covaried directly with Cu binding-site densities in DOM. However, no aspect of Cu–DOM complexation consistently covaried with fluorophores (i.e., the fluorescence index) or low molecular weight organic acids. Our results suggest that global increases in UV radiation will affect Cu–DOM complexation and subsequent Cu toxicity depending on light regime as well as DOM source. Handling editor: K. Martens     

冻融条件和土壤湿度对森林土壤渗漏液溶解性有机质含量与光谱结构特征的影响

土壤溶解性有机质(DOM)含量及其稳定性影响土壤碳氮循环关键过程,目前气候变化下森林土壤DOM含量及其光谱结构特征仍不明确.本研究利用长白山阔叶红松混交林和次生白桦林表层土壤进行室内冻融模拟试验,结合三维荧光光谱-平行因子分析方法,研究冻融强度和冻融循环次数及其交互作用对不同湿度温带森林土壤渗漏液DOM含量、组分和光谱结构特征的影响.结果表明: 森林土壤渗漏液DOM含量及其组分因林分类型、土壤湿度、冻融强度、冻融循环次数不同而存在差异.2种林分土壤渗漏液DOM含量均在中湿度下最低,并受高强度冻融影响显著,且随冻融循环次数增加呈现先增加后降低的趋势.可鉴别DOM的3个荧光组分:胡敏酸类DOM、富里酸类DOM和蛋白类DOM;阔叶红松混交林土壤渗漏液DOM组分以富里酸类物质为主,腐殖化程度较高;而次生白桦林土壤渗漏液DOM组分以胡敏酸类物质为主,3组分受冻融强度显著影响,稳定性较低.经冗余分析(RDA)发现,林分在很大程度上决定森林土壤DOM属性变化,次生白桦林土壤渗漏液DOM含量及其3组分荧光强度大于阔叶红松混交林;土壤湿度显著影响DOM芳香性,2种林分土壤渗漏液DOM芳香性均呈中湿度>高湿度>低湿度的趋势;随冻融强度增加,阔叶红松混交林土壤渗漏液DOM芳香性显著降低;多次冻融循环显著提高2种林分土壤渗漏液DOM腐殖化程度.因此,不同冻融作用下,低湿度温带森林土壤渗漏液DOM含量及其生物有效性呈现增加的趋势,尤其是次生白桦林土壤,可能会增加春季冻融期温带森林土壤溶解性有机质淋溶损失.这些结果可为深入研究野外冻融期温带森林土壤溶解性有机质周转机制提供参考.     

Dissolved Organic Matter Characteristics Across a Subtropical Wetland’s Landscape: Application of Optical Properties in the Assessment of Environmental Dynamics

Wetlands are known to be important sources of dissolved organic matter (DOM) to rivers and coastal environments. However, the environmental dynamics of DOM within wetlands have not been well documented on large spatial scales. To better assess DOM dynamics within large wetlands, we determined high resolution spatial distributions of dissolved organic carbon (DOC) concentrations and DOM quality by excitation–emission matrix spectroscopy combined with parallel factor analysis (EEM–PARAFAC) in a subtropical freshwater wetland, the Everglades, Florida, USA. DOC concentrations decreased from north to south along the general water flow path and were linearly correlated with chloride concentration, a tracer of water derived from the Everglades Agricultural Area (EAA), suggesting that agricultural activities are directly or indirectly a major source of DOM in the Everglades. The optical properties of DOM, however, also changed successively along the water flow path from high molecular weight, peat-soil and highly oxidized agricultural soil-derived DOM to the north, to lower molecular weight, biologically produced DOM to the south. These results suggest that even though DOC concentration seems to be distributed conservatively, DOM sources and diagenetic processing can be dynamic throughout wetland landscapes. As such, EEM–PARAFAC clearly revealed that humic-enriched DOM from the EAA is gradually replaced by microbial- and plant-derived DOM along the general water flow path, while additional humic-like contributions are added from marsh soils. Results presented here indicate that both hydrology and primary productivity are important drivers controlling DOM dynamics in large wetlands. The biogeochemical processes controlling the DOM composition are complex and merit further investigation.     

Dissolved Organic Matter Concentration and Quality Influences upon Structure and Function of Freshwater Microbial Communities

Past studies have suggested that the concentration and quality of dissolved organic matter (DOM) may influence microbial community structure. In this study, we cross-inoculated the bacterial communities from two streams and a dystrophic lake that varied in DOM concentration and chemistry, to yield nine fully crossed treatments. We measured dissolved organic carbon (DOC) concentration and heterotrophic microbial community productivity throughout a 72-h incubation period, characterized DOM quality by molecular weight, and determined microbial community structure at the initial and final time points. Our results indicate that all bacterial inoculate sources had similar effects upon DOC concentration and DOM quality, regardless of the DOM source. These effects included an overall decrease in DOM M _W and an initial period of DOC concentration variability between 0-24h. In contrast, microbial communities and their metabolic rates converged to profiles that reflected the DOM source upon which they were growing, regardless of the initial bacterial inoculation. The one exception was that the bacterial community from the low-concentration and low-molecular-weight DOM source exhibited a greater denaturing gradient gel electrophoresis (DGGE) band richness when grown in its own DOM source than when grown in the highest concentration and molecular weight DOM source. This treatment also exhibited a higher rate of productivity. In general, our data suggest that microbial communities are selected by the DOM sources to which they are exposed. A microbial community will utilize the low-molecular-weight (or labile) DOM sources as well as parts of the high-molecular-weight (refractory) DOM, until a community develops that can efficiently metabolize the more abundant high-molecular-weight source. This experiment examines some of the complex interactions between microbial community selection and the combined factors of DOM quality and concentration. Our data suggest that the roles of aerobic aquatic heterotrophic bacteria in carbon cycling, as well as the importance of high-molecular-weight DOM as a carbon source, may be more complex than is conventionally recognized.     

Characterization and origin of polar dissolved organic matter from the Great Salt Lake

Polar dissolved organic matter (DOM) was isolated from a surface-water sample from the Great Salt Lake by separating it from colloidal organic matter by membrane dialysis, from less-polar DOM fractions by resin sorbents, and from inorganic salts by a combination of sodium cation exchange followed by precipitation of sodium salts by acetic acid during evaporative concentration. Polar DOM was the most abundant DOM fraction, accounting for 56% of the isolated DOM. Colloidal organic matter was ¹⁴C-age dated to be about 100% modern carbon and all of the DOM fractions were ¹⁴C-age dated to be between 94 and 95% modern carbon. Average structural models of each DOM fraction were derived that incorporated quantitative elemental and infrared, ¹³C-NMR, and electrospray/mass spectrometric data. The polar DOM model consisted of open-chain N-acetyl hydroxy carboxylic acids likely derived from N-acetyl heteropolysaccharides that constituted the colloidal organic matter. The less polar DOM fraction models consisted of aliphatic alicyclic ring structures substituted with carboxyl, hydroxyl, ether, ester, and methyl groups. These ring structures had characteristics similar to terpenoid precursors. All DOM fractions in the Great Salt Lake are derived from algae and bacteria that dominate DOM inputs in this lake.     

Dissolved organic matter (DOM) concentration and quality in a forested mid-Atlantic watershed, USA

Understanding the quantity and quality of dissolved organic matter (DOM) in potential watershed sources is critical for explaining and quantifying the exports of DOM in stream runoff. Here, we examined the concentration and quality of DOM for ten watershed sources in a 12?ha forested catchment over a two-year period. DOM composition was evaluated for: throughfall, litter leachate, soil water (zero and tension), shallow and deep groundwater, stream water, hyporheic zone, and groundwater seeps. DOM quality was measured using a suite of optical indices including UV–visible absorbance and PARAFAC modeling of fluorescence excitation-emission matrices (EEMs). DOM concentrations and quality displayed a pronounced trend across watershed sources. Surficial watershed sources had higher DOM concentrations and more humic-like DOM with higher molecular weight whereas deeper groundwater sources were rich in % protein-like fluorescence. The greater % contribution of protein-like fluorescence in groundwater suggested that a larger fraction of groundwater DOM may be bioavailable. DOM for wetland groundwater was more aromatic and humic-like than that at the well-drained riparian location. Principal component analyses (PCA) revealed that the differences in surficial watershed compartments were dictated by humic-like components while groundwater sources separated out by % protein-like fluorescence. Observations from optical indices did not provide any conclusive evidence for preferential association of dissolved organic carbon (DOC) or dissolved organic nitrogen (DON) with any particular DOM quality pools.     

Ecosystem processes drive dissolved organic matter quality in a highly dynamic water body

The complexity and variability of processes determining dissolved organic matter (DOM) quality is likely to increase in highly dynamic systems such as Mediterranean water bodies. We studied the dynamics of DOM in a Mediterranean lagoon dominated by seasonal submerged vegetation and receiving torrential freshwater inputs. In order to trace changes in DOM quality throughout the year in relation with potential DOM sources, we used spectroscopic techniques including UV–visible absorbance and fluorescence excitation–emission matrices. The quality of the lagoon DOM fluctuates on a seasonal basis between the characteristics of torrential inputs and macrophytes. Humification and aromaticity of DOM increased markedly after the torrential inputs of materials derived from terrestrial vegetation and soils in the catchment. The macrophytes in the lagoon contributed with less humified materials and protein-like compounds. Other minor processes such as seawater entrances, photodegradation or temporary bottom hypoxia translated into sporadic DOM quality changes. These results highlight the need of a whole ecosystem approach to understand changes in DOM quality due to ecosystem processes that might otherwise be exclusively attributed to DOM reactivity.     

陆地生态系统中水溶性有机物动态及其环境学意义

水溶性有机物(DOM)是陆地生态系统中最活跃的有机碳库,也是土壤圈层与相关圈层进行物质与能量交换的重要表现形式,它对重金属、养分元素和有机污染物的活化、迁移与生态毒性有较大影响,在农业土壤溶液中DOM浓度通常在10～80mgC·L^-1,湿地土壤中多数在25～50mgC·L^-1,与森林土壤剖面淋滤水中的DOM相近,但在某些微域土壤环境(如根际和有机肥施用点附近)中DOM浓度可高达200～1000mgC·L^-1,不同来源的DOM在土壤中的迁移性与降解性明显不同,含低分子量组分或亲水性组分较多的DOM不易被土壤吸持而易被微生物降解,pH值相对较高的土壤(如石灰性土壤)对DOM吸附较弱,但pH较低和含有大量氧化物的土壤(如红壤、赤红壤和砖红壤等)则对DOM的吸附较强,施用石灰、土壤淹水或干湿交替、温度升高等有利于土壤保持较高的DOM浓度,由于DOM-金属配合物的形成,DOM能明显促进土壤重金属活化和向下迁移,而且DOM中低分子量或亲水性组分所占比例越低活化作用越强,同样地,由于DOM具有两亲性质,也能明显提高疏水性有机污染物(如农药和持久难降解有机污染物)的水溶性,增加其对环境污染的风险,特别是含疏水性组分越多的DOM这种作用越强．可以认为,继续加强有关DOM在陆地生态系统中产生与消长规律,特别是DOM及其与污染物的配合物从陆地生态系统向水体迁移的机理及其通量的研究,对合理预测污染物的环境行为和科学地进行环境风险评估有重要意义。     

Photo-biochemical transformation of dissolved organic matter on the surface of the coastal East Antarctic ice sheet

Recent studies have highlighted the composition and complexity of dissolved organic matter (DOM) in glacial environments. Climate-induced changes to glacier runoff are projected to be an important source of DOM to coastal ecosystems. Photochemical and microbial (termed photo-biochemical) degradation of DOM would determine its fate on the glacier surface and in recipient coastal ecosystems. In order to understand the molecular imprints of photo-biochemical alteration of DOM, in situ field experiments were conducted over a period of 35 days in a coastal Antarctic site and DOM molecularly characterised using ultrahigh-resolution mass spectrometry. We show that the biogeochemistry of DOM is highly complex and intimately connected with microbial and photochemical processes operating individually or in combination. Photo-biochemical processes resulted in shifts in the nitrogen, sulfur, and phosphorous content of the DOM. These processes are also an important mechanism for transforming refractory DOM, like dissolved black carbon and carboxylic rich alicyclic molecules from the snow surface. This study is unique, as it provides new molecular-level information on compounds that comprise the photo- and bio-labile, photo- and bio-refractory, as well as photo- and bio-produced fractions of the supraglacial DOM pool. These insights into the interactions between microbes, light, and specific components of the DOM pool highlight the need for studies focused on the biogeochemistry of supraglacial carbon and its response to a changing climate.     

溶解性有机质对土壤中有机污染物环境行为的影响

土壤中溶解性有机质(DOM)是生物活性和物理化学反应活性都很活跃的有机组分,主要通过疏水吸附、分配、氢键、电荷转移、共价键、范德华力等多种作用与有机污染物结合,提高溶液中有机污染物的溶解度,改变土壤中有机污染物的吸附-解吸、迁移-转化等环境行为．DOM对有机污染物的吸附-解吸、迁移-转化过程的影响有双重性：一方面,DOM与有机污染物在土壤表面的共吸附可增加土壤对有机污染物的吸附容量,促进有机污染物在土壤中的吸持;另一方面,DOM对有机污染物的增溶作用,有利于土壤中有机污染物的解吸,提高移动性．作为光敏剂,DOM能提高土壤中有机物的光解反应速率．在一定条件下,DOM也可影响土壤中有机污染物的水解过程．DOM对土壤中有机污染物环境行为的影响与DOM和有机污染物的性质及其相互作用的介质条件密切相关．     

水溶性有机质对土壤中镉吸附行为的影响

水溶性有机质 (DOM)是陆地生态系统和水生生态系统中的一种很活跃的组分 .本文以赤红壤、水稻土和褐土作为供试土壤 ,研究了来源于稻秆和底泥的DOM对土壤中Cd吸附行为的影响 .DOM对土壤中Cd的吸附行为具有明显的抑制作用 .这种抑制作用与土壤类型和DOM种类有关 .在 3种供试土壤中 ,无论添加稻秆DOM还是底泥DOM ,都会使Cd的最大吸附容量和吸附率明显降低 ,其下降幅度为17 3%～ 93 9%.在添加同一种DOM的前提下 ,DOM对Cd吸附的抑制作用均为 :赤红壤 >水稻土 >褐土 .如果不添加DOM ,则土壤对Cd的最大吸附容量主要取决于土壤固相的吸附特性 ,添加DOM后土壤对Cd的最大吸附容量则主要取决于液相中的DOM .由此推断 ,传统的看法 ,通过施用有机肥来固定土壤中的Cd并达到治理重金属污染土壤的观点值得商榷 .     

Designer drug 2,5-dimethoxy-4-methyl-amphetamine (DOM, STP): involvement of the cytochrome P450 isoenzymes in formation of its main metabolite and detection of the latter in rat urine as proof of a drug intake using gas chromatography-mass spectrometry

The designer drug 2,5-dimethoxy-4-methyl-amphetamine (DOM, STP) is known to be extensively metabolized in various species. The current study showed that cytochrome P450 2D6 was the only isoenzyme involved in formation of the main metabolite hydroxy DOM. In addition, the authors' systematic toxicological analysis (STA) procedure using full-scan GC-MS was suitable to prove an intake of a common drug users' dose of DOM by detection of hydroxy DOM in rat urine. Assuming similar metabolism, the described STA procedure should be suitable for proof of an intake of DOM in human urine. However, DOM and/or other metabolites such as deamino-oxo-hydroxy DOM might be the target analyte in urine of CYP2D6 poor metabolizers.     

Characterisation and reactivity continuum of dissolved organic matter in forested headwater catchments of Andean Patagonia

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Dissolved organic matter status in Damietta estuary of the Nile

The seasonal distribution of dissolved organic matter (DOM) in Damietta estuary of the Nile was investigated to show the influence of organic pollution. The DOM values increased generally with depth. The vertical values of DOM varied from 0.23-9.97 mg O/l. The average DOM values gave noticeable local variations in each month and pronounced monthly variations at each station. The maximum monthly average value in August coincided principally with elevation of temperature and the minimum in December is due mainly to the drop in temperature. The direct effect of pollution, in increasing the DOM content in the estuary, decreases relatively towards the sea, as indicated by the minimum regional average DOM value at the mouth of Damietta estuary. An inverse relationship was found generally between the averages of DOM and those of dissolved oxygen.     

Characterization of dissolved organic matter under contrasting hydrologic regimes in a subtropical watershed using PARAFAC model

Dissolved organic matter (DOM) was characterized during five basin-scale investigations (either after storms or in droughts) in Jiulong River, China that is affected by the Asian Monsoon, tropical storms and anthropogenic activities. Dissolved organic carbon concentration, DOM absorption and fluorescence (excitation-emission matrix spectra, EEMs) were measured. Parallel factor analysis (PARAFAC) of EEMs identified three humic-like and two protein-like fluorescent components. DOM concentration was highest at two polluted stations in droughts while lowest in pristine headwaters (station N1). DOM concentration increased most evidently after storms in May, 2009, indicating effective flushing of DOM from land to the river close to the onset of flood season. The protein-like fraction in PARAFAC results decreased after storms in May and June, 2009, highlighting changes in DOM composition and thus its environmental role. Dam constructions likely increased the residence time of DOM in river, making the inflow of DOM during storms have more implications for the riverine (in comparison with estuarine) biogeochemical processes. The effect of storm in August, 2008 after intense DOM flushing during several preceding storms, was not evident. A severe dinoflagellate algal bloom occurred during the extreme drought in the lower watershed, which increased DOM concentration and the protein-like fraction at impacted stations. Different DOM compositions during and after algal bloom were discriminated using the two protein-like components. This study demonstrates the importance of hydrologic regimes and anthropogenic activities on freshwater DOM and its environmental role, which has implications for a number of other rivers that share similar characteristics.     

Beneficial and detrimental interactive effects of dissolved organic matter and ultraviolet radiation on Zooplankton in a transparent lake

While changes in dissolved organic matter (DOM) concentrations are expected to affect zooplankton species through attenuation of potentially damaging ultraviolet (UV) radiation, generation of potentially beneficial or harmful photoproducts, pH alteration, and microbial food web stimulation, the combined effects of such changes on zooplankton community structure have not been studied previously. Our purpose was to determine how an increase in allochthonous DOM and associated changes in pH in an initially transparent lake may affect zooplankton community structure, and how exposure to solar UV may alter these DOM and pH effects. We ran microcosm experiments manipulating UV, DOM, and pH near the surface of Lake Giles in northeastern Pennsylvania. We found that when DOM was added in the presence of ambient UV, Daphnia and copepod UV-mortality was reduced by approximately three and two times compared to UV exposure without extra DOM. When DOM was added in the absence of UV, adult Daphnia and copepods were reduced compared to no DOM addition in the absence of UV. Daphnia and cyclopoid egg production and rotifer abundance were generally higher in the presence of DOM, regardless of UV treatment. The lower abundance yet high egg production in the presence of DOM and absence of UV may be explained by higher abundance of egg-bearing adults compared to non-egg-bearers. We conclude that allochthonous DOM benefits some zooplankton in a high-UV environment, but may be detrimental under low-UV conditions. Overall, Daphnia abundance and egg production were higher than that of calanoid copepods in the DOM additions, indicating that in some lakes an increase in allochthonous DOM may lead to a zooplankton community shift favoring Daphnia over calanoid copepods.     

Spatial and temporal variability of dissolved organic matter quantity and composition in an oligotrophic subtropical coastal wetland

Dissolved organic matter (DOM) is an essential component of the carbon cycle and a critical driver in controlling variety of biogeochemical and ecological processes in wetlands. The quality of this DOM as it relates to composition and reactivity is directly related to its sources and may vary on temporal and spatial scales. However, large scale, long-term studies of DOM dynamics in wetlands are still scarce in the literature. Here we present a multi-year DOM characterization study for monthly surface water samples collected at 14 sampling stations along two transects within the greater Everglades, a subtropical, oligotrophic, coastal freshwater wetland-mangrove-estuarine ecosystem. In an attempt to assess quantitative and qualitative variations of DOM on both spatial and temporal scales, we determined dissolved organic carbon (DOC) values and DOM optical properties, respectively. DOM quality was assessed using, excitation emission matrix (EEM) fluorescence coupled with parallel factor analysis (PARAFAC). Variations of the PARAFAC components abundance and composition were clearly observed on spatial and seasonal scales. Dry versus wet season DOC concentrations were affected by dry-down and re-wetting processes in the freshwater marshes, while DOM compositional features were controlled by soil and higher plant versus periphyton sources respectively. Peat-soil based freshwater marsh sites could be clearly differentiated from marl-soil based sites based on EEM–PARAFAC data. Freshwater marsh DOM was enriched in higher plant and soil-derived humic-like compounds, compared to estuarine sites which were more controlled by algae- and microbial-derived inputs. DOM from fringe mangrove sites could be differentiated between tidally influenced sites and sites exposed to long inundation periods. As such coastal estuarine sites were significantly controlled by hydrology, while DOM dynamics in Florida Bay were seasonally driven by both primary productivity and hydrology. This study exemplifies the application of long term optical properties monitoring as an effective technique to investigate DOM dynamics in aquatic ecosystems. The work presented here also serves as a pre-restoration condition dataset for DOM in the context of the Comprehensive Everglades Restoration Plan (CERP).