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 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.     

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).     

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。     

土壤中水溶性有机质及其对重金属化学与生物行为的影响

土壤水溶性有机质是陆地生态系统和水生生态系统中一种重要的、很活跃的化学组分,已成为环境科学、土壤学和生态学等学科的研究热点．土壤DOM对重金属化学与生物行为有重要影响。但其机理尚不清楚．文中从土壤性质、环境条件、人为因素等方面阐述了土壤DOM产生及影响因素,总结评述了DOM对重金属化学行为和生物有效性的影响,将DOM对重金属的影响机制归纳为络合机制、竞争吸附机制、酸碱缓冲机制．在此基础上,提出了DOM研究存在的问题及其展望．     

Diurnal changes in dissolved organic and inorganic carbon and nitrogen in a hardwater stream

Organic and inorganic carbon and nitrogen parameters were sampled simultaneously at 6 h intervals over a diurnal period at seven stations in a small hardwater stream in southern Michigan. Concentrations and budget values (kg/day) varied up to 10-fold at individual stations and between stations. The most constant parameters were total dissolved organic carbon and nitrogen. The most variable parameter was particulate organic carbon. Significant changes were noted in all parameters as the stream passed through different stream-side habitats. Budget values facilitated interpretation of these changes over time between stations. High variability in the concentration values was introduced by large allochthonous inputs of dissolved organic matter (DOM) and water alternately adding to or diluting parameters. Distance from upstream terrestrial DOM sources, DOM residence time, the pulsed nature of DOM inputs and biological utilization of DOM have important effects on the quality and quantity of DOM that enters recipient lakes and rivers. The importance of ground-water flux and DOM content is stressed. The DOM input and turnover within hardwater streams appears t o be in rapid, dynamic equilibrium.     

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.     

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.     

Measuring the influence of environmental conditions on dissolved organic matter biodegradability and optical properties: a combined field and laboratory study

Fluorescence spectroscopy is a common tool to assess optical dissolved organic matter (DOM) and a number of characteristics, including DOM biodegradability, have been inferred from these analyses. However, recent findings on soil and DOM dynamics emphasize the importance of ecosystem-scale factors, such as physical separation of substrate from soil microbial communities and soil physiochemical cycles driving DOM stability. We apply this principle to soil derived DOM and hypothesize that optical properties can only supply information on biodegradability when evaluated in the larger ecosystem because substrate composition and the activity/abundance of the microbial community ultimately drive DOM degradation. To evaluate biodegradability in this context, we assessed aqueous soil extracts for water extractable organic carbon (WEOC) content, biodegradability, microbial biomass and DOM characteristics using fluorescence spectroscopy across a range of environmental conditions (covariant with season and land use) in northern Vermont, USA. Our results indicate that changes in environmental conditions affect composition, quantity, and biodegradability of DOM. WEOC concentrations were highest in the fall and lowest in the summer, while no significant differences were found between land covers; however, DOM biodegradability was significantly higher in the agricultural site across seasons. Despite a shift in utilized substrate from less aromatic DOM in summer to more aromatic DOM in winter, biodegradability was similar for all seasons. The only exception was cold temperature incubations where microbial activity was depressed, and processing was slowed. These results provide examples on how fluorescence based metrics can be combined with context relevant environmental parameters to evaluate bioavailability in the context of the larger ecosystem.

     

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 .     

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

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Role of aging on growth hormone and prolactin release after growth hormone-releasing hormone and domperidone in man

Growth hormone (GH) and prolactin (PRL) secretion after GH-releasing hormone (GHRH) and domperidone (DOM), an antidopaminergic drug which does not cross the blood-brain barrier (BBB), was evaluated in 8 healthy elderly men (65-91 years) and in 7 young adults (23-40 years). All received in random order at 2-day intervals: GHRH(1-40) (50 micrograms i.v.) bolus, DOM (5 mg/h) infusion, GHRH(1-40) (50 micrograms i.v.) plus DOM (5 mg/h i.v.), saline solution. In elderly men GH increase after GHRH was significantly lower than in young men. DOM alone did not change GH secretion in either of these groups, whereas it increased the GH response to GHRH only in young adults. PRL levels increased in both young and elderly men during both DOM and GHRH plus DOM, but the PRL release was more marked in young than in elderly men. Both integrated secretion of GH after GHRH and of PRL after DOM were inversely correlated to chronological age. Our data show an impairment of GH rise after GHRH and of PRL after DOM in elderly adults. It is also stressed that peripheral blockade of dopamine receptors by DOM is unable to amplify the GH response to GHRH only in elderly men. A reduction in GH release after GHRH might be related to aging, perhaps through a reduction of dopaminergic tonus.     

Role of ultraviolet-B radiation on bacterioplankton and the availability of dissolved organic matter

Attenuation of ultraviolet (UV)-radiation into the water column is highly correlated with the concentration of the dissolved organic matter (DOM). Thus UV penetrates deeper into marine waters than into freshwater systems. DOM is efficiently cleaved by solar surface radiation levels consuming more oxygen than bacterial metabolism. This photolytically cleaved DOM exhibits higher absorbance ratios (250/365 nm) than untreated DOM. Natural bacterioplankton reach higher abundance if inoculated in previously solar-exposed DOM than in untreated DOM; during bacterial growth the absorbance ratio declines steadily indicating the utilization of the photolytically cleaved DOM. On the other hand, bacterioplankton are greatly reduced in their activity if exposed to surface solar radiation levels. Photoenzymatic repair of DNA induced by UV-A radiation, however, leads to an efficient recovery of bacterial activity once the UV-B stress is released. Turbulent mixing of the upper layers of the water column leads to a continuous alteration of the UV exposure regime. Close to the surface, bacteria and DOM are exposed to high levels of UV-B leading to a reduction in bacterial activity and to photolysis of DOM. Once mixed into deeper layers where UV-B is attenuated, but sufficient UV-A is remaining to allow photoenzymatic repair, the photolytically cleaved DOM is efficiently taken up by bacterioplankton leading to even higher bacterial activity than prior to the exposure. Thus, the overall effect of UV on bacterioplankton is actually an enhancement of bacterial activity despite their lack of protective pigments.     

Relationships Between Land Cover and Dissolved Organic Matter Change Along the River to Lake Transition

Dissolved organic matter (DOM) influences the physical, chemical, and biological properties of aquatic ecosystems. We hypothesized that controls over spatial variation in DOM quantity and composition (measured with DOM optical properties) differ based on the source of DOM to aquatic ecosystems. DOM quantity and composition should be better predicted by land cover in aquatic habitats with allochthonous DOM and related more strongly to nutrients in aquatic habitats with autochthonous DOM. Three habitat types [rivers (R), rivermouths (RM), and the nearshore zone (L)] associated with 23 tributaries of the Laurentian Great Lakes were sampled to test this prediction. Evidence from optical indices suggests that DOM in these habitats generally ranged from allochthonous (R sites) to a mix of allochthonous-like and autochthonous-like (L sites). Contrary to expectations, DOM properties such as the fluorescence index, humification index, and spectral slope ratio were only weakly related to land cover or nutrient data (Bayesian R ² values were indistinguishable from zero). Strongly supported models in all habitat types linked DOM quantity (that is, dissolved organic carbon concentration [DOC]) to both land cover and nutrients (Bayesian R ² values ranging from 0.55 to 0.72). Strongly supported models predicting DOC changed with habitat type: The most important predictor in R sites was wetlands whereas the most important predictor at L sites was croplands. These results suggest that as the DOM pool becomes more autochthonous-like, croplands become a more important driver of spatial variation in DOC and wetlands become less important.     

Synergy of Fresh and Accumulated Organic Matter to Bacterial Growth

The main goal of this research was to evaluate whether the mixture of fresh labile dissolved organic matter (DOM) and accumulated refractory DOM influences bacterial production, respiration, and growth efficiency (BGE) in aquatic ecosystems. Bacterial batch cultures were set up using DOM leached from aquatic macrophytes as the fresh DOM pool and DOM accumulated from a tropical humic lagoon. Two sets of experiments were performed and bacterial growth was followed in cultures composed of each carbon substrate (first experiment) and by carbon substrates combined (second experiment), with and without the addition of nitrogen and phosphorus. In both experiments, bacterial production, respiration, and BGE were always higher in cultures with N and P additions, indicating a consistent inorganic nutrient limitation. Bacterial production, respiration, and BGE were higher in cultures set up with leachate DOM than in cultures set up with humic DOM, indicating that the quality of the organic matter pool influenced the bacterial growth. Bacterial production and respiration were higher in the mixture of substrates (second experiment) than expected by bacterial production and respiration in single substrate cultures (first experiment). We suggest that the differences in the concentration of some compounds between DOM sources, the co-metabolism on carbon compound decomposition, and the higher diversity of molecules possibly support a greater bacterial diversity which might explain the higher bacterial growth observed. Finally, our results indicate that the mixture of fresh labile and accumulated refractory DOM that naturally occurs in aquatic ecosystems could accelerate the bacterial growth and bacterial DOM removal.     

Pesticide desorption from soils facilitated by dissolved organic matter coming from composts: experimental data and modelling approach

Dissolved organic matter (DOM) interaction with pesticides was examined studying the ability of DOM to desorb 8 pesticides previously sorbed to soil. DOM was originating from municipal waste composts at two maturity degrees, recovered at 20°C and by hot-pressurised subcritical water. Pesticide desorption depended on their previous sorption on soil. When sorption was low (K_OC ≤ 50, sulcotrione, metalaxyl), water was more efficient than DOM for desorption. On the contrary, when sorption was high (K_OC ≥ 2000, trifluraline), little effect of DOM was observed. For the moderately sorbed pesticides, DOM favoured pesticide desorption compared to water. For the lowest sorbed pesticides (K_OC ≤ 100), hysteresis was increased with larger proportions of DOM extracted with subcritical-water. Dissolved organic matter extracted from fresh-immature compost had larger capacity to mobilize the sorbed pesticides than the DOM from the mature compost. The pesticide desorption resulted from the positive and competitive interactions between pesticide, DOM and soil surfaces. These interactions were modelled considering separate partitioning coefficients. A general equation allowed the deduction of specific coefficients describing interactions in solution between pesticides and the non-sorbed fraction of DOM remaining in solution. This fraction was supposed to contain the most hydrophilic fraction of DOM and was able to interact with the most polar pesticide (amitrol). When pesticide hydrophobicity increased, the partitioning between pesticide and DOM decreased. Modelling the three-phase system (liquid, DOM and solid phases) pointed out that the solid phase played the most important role on pesticide behaviour through the sorption process of DOM and pesticides.