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.     

Absorption properties of dissolved organic matter in East Asian temperate lakes

Limnology - There are few comparative studies of chromophoric dissolved organic matter (CDOM) in humid temperate lakes. In this study, we examined the ultraviolet absorption of water sampled from...     

不同有机物料的蚯蚓堆肥及可溶性有机物的三维荧光光谱特征

研究了牛粪、茶渣、药渣和菌渣等有机物料的不同复配比例的蚯蚓生长状况,筛选出适合蚯蚓生长的最佳物料配比,并进一步分析了这些适合蚯蚓生长的物料配比处理的养分含量和三维荧光光谱特征的动态变化.结果表明： 牛粪与药渣、牛粪与茶渣的不同配比物料中的蚯蚓生长情况均较好,而有菌渣复配的物料的蚯蚓生长情况较差;随着堆肥时间的增加,堆肥的pH逐步趋向中性和弱酸性,堆肥的电导率、全氮、全磷、速效氮和速效磷含量逐渐增加,全钾和速效钾呈现出先增加后降低的趋势,而堆肥的有机质含量逐渐减小;三维荧光光谱特征和荧光区域指数结果表明,随堆肥时间增加,可溶性有机物(DOM)中的类蛋白峰逐渐减弱,而类腐殖质峰逐渐增强.蚯蚓堆肥改变了有机废弃物的DOM组成,生成了大量类胡敏酸和类富里酸物质, 性质逐渐趋于稳定.因此,有机废弃物蚯蚓堆肥中DOM物质含量变化可作为蚯蚓堆肥成熟度的评估指标.     

Long term records of riverine dissolved organic matter

This presents the longest, consistent records of dissolved organic carbon in rivers ever published. This study presents long-term records of organic matter as indicated by water colour that were constructed for three catchments in Northern England for as far back as 1962. Observations show that there have been large increases in DOC concentrations over the period of study with in one case a doubling of the concentration over a period of 29 years. However, in one of the catchments no significant change was observed over a 31-year period. All catchments show common inter-annual control on carbon release in response to droughts, but no step increases in DOC concentrations were observed in response to such perturbations with pre-drought levels being restored within a period 3–4 years. Observed increasing trends do not correlate with changes in river discharge, pH, alkalinity or rainfall, but do coincide with increasing average summer temperatures in the region. The times series of DOC concentration over the period of the record appears stationary, but the distribution of daily values suggests a change in sources of colour over the increasing trend. The evidence supports a view that increases in carbon release are in equilibrium with temperature increases accentuated by land-use factors.     

Complexation between Hg(II) and dissolved organic matter in stream waters: an application of fluorescence spectroscopy

Complexation between Hg(II) and dissolved organic matter (DOM) collected from streams in Ontario, Canada, was studied using three-dimensional excitation emission matrix (3DEEM) fluorescence spectroscopy. The results show that DOM reacted with Hg(II) rapidly, and the complexation reached pseudo-equilibrium within 20 s. Maximum excitation/emission (Ex/Em) wavelengths shifted towards the longer wavelengths, indicating that DOM structure changed during its interaction with Hg(II). Using fluorescence quenching titrations, complexing parameters, conditional stability constants and the percentage of fluorophores participating in the complexation, were estimated by the modified Stern–Volmer equation. The experimental and field survey results suggest that the Hg–DOM complexation in various streams was related to water quality parameters, e.g. DOC, Cl–, and cation concentrations, and was strongly affected by UV irradiation.     

Soil microbial activity in relation to dissolved organic matter properties under different tree species

Background and aims

The total concentration of dissolved organic carbon (DOC) has often been observed to correlate positively with soil microbial respiration. The aim was to explain the correlation with the properties of dissolved organic matter (DOM).

Methods

A dataset from previously published papers was gathered together and subjected to multivariate analyses. Samples were collected from five tree species experiments in Finland. The degradability of DOM was assessed by measuring bacterial and fungal growth in DOM. The chemical properties of DOM were assessed by XAD resin fractionation and molecular weight. Soil microbial activity was assessed as C and N mineralization and microbial biomass.

Results

Both low and high molecular weight compounds, as well as hydrophilic neutral compounds, seemed to be relatively easily degradable. In contrast to our presupposition, easily degradable DOM seemed to be less abundant in soil where variables describing microbial activity were higher. Birch soil with higher microbial biomass N seemed to contain less easily degradable DOM than spruce soil.

Conclusion

We suggest that DOM collected and characterized at a certain point reflects more the accumulation of refractory compounds following high microbial activity than the easily degradable compounds that microbes would be using when measured.

     

Microbial transformation of labile dissolved organic matter into humic-like matter in seawater

Abstract Microbial transformation of labile, low molecular weight dissolved organic matter (DOM) into dissolved humic matter (DHM) was studied in seawater. Surface water samples were amended with [¹⁴C into ¹⁴CO₂, TO¹⁴C (total organic ¹⁴C), and PO¹⁴C (particulate organic ¹⁴C), was measured over time in confined samples. The humic and non-humic fractions of DO¹⁴C (dissolved organic ¹⁴C) were separated according to a common operational definition of DHM based on adsorption on XAD-8 macroporous resin. Both TO¹⁴C and non-humic DO¹⁴C decreased during the experiments. However, ¹⁴C-labelled DHM increased during the first week of the incubations, to a level where it comprised 15% of the TO¹⁴C remaining in the samples, or 3% of the initially added ¹⁴C. Towards the end of experiments (ca 70 days), the humic fraction of DO¹⁴C gradually approached the background level of poisoned control samples. Provided that the XAD-8 operational definition of DHM is accepted, this study indicates that humic matter may be formed in seawater within days from labile monomers such as glucose.     

Instream release of dissolved organic matter from coarse and fine particulate organic matter of different origins

Dissolved organic matter (DOM), produced through leaching from particulate organic matter (POM), is an essential component of the carbon cycle in streams. The present study investigated the instream DOM release from POM, varying in size and chemical quality. We produced large and medium sized fine particulate organic matter (L-FPOM, 250–500 μm; M-FPOM, 100–250 μm) of defined quality by feeding five types of coarse particulate organic matter (CPOM) to shredding amphipods (Gammarus spp.). Microscopic observations showed that L-FPOM and M-FPOM mainly consisted of the fecal pellets of amphipods, and incompletely eaten plant fragments, respectively. DOM release experiments were conducted by exposing CPOM and M- and L-FPOM fractions in natural stream water over a two week period. For CPOM, the release of dissolved organic carbon (DOC) by leaching was highest during the first 6 h (3.64–23.9 mg C g C^?1 h^?1) and decreased rapidly afterwards. For M- and L-FPOM, the DOC release remained low during the entire study period (range: 0.008–0.15 mg C g C^?1 h^?1). Two-way ANOVA revealed that the DOC release rate significantly differed with POM source and size fraction, both at day 1 and after a week of exposure. Multiple regression analyses revealed a significant correlation of elemental contents and lignin content to DOC release rate after a week of exposure. Overall, the results indicated that DOC release rate of FPOM, on a carbon basis, is comparable to that of CPOM after leaching, while size and source of POM significantly affect DOC release rate.     

土壤溶解性有机质的特性与环境意义

土壤生态环境是一个复杂的多介质多界面体系,尽管关于土壤溶解性有机质 研究还不完善,但现有的研究表明,它是这一环境中最为活跃的化学组成之一。由于土壤溶解性有机质在C、N、P和S等营养元素的生物地球化学过程、成土过程、微生物的生长代谢过程、土壤有南分解和转化过程以及土壤污染物的迁移过程有着重要的作用,因此已成为土壤科学、生态科学和环境科学交叉领域的研究热点,本文从土壤溶解性有机质的提取方法、来源、组成、含量和影响因素、生物有效性及环境意义等方面的研究进展作了简要的论述,同时提出了未来的研究方向。     

Photo-oxidation of dissolved organic matter for trace metal analysis

Abstract

Photo-oxidation of dissolved organic matter in saline and non- saline samples is monitored by measurement of residual fluorescence intensity. For fulvic acids, the method has a detection limit of 0.005 mg C L^?1, and maximum photo-oxidation is achieved with H₂O₂ oxidant and a low-intensity UV source.     

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     

Acclimation of stream-bed heterotrophic microflora: metabolic responses to dissolved organic matter

SUMMARY.

• 1 Studies were performed to assess the acclimation of the stream-bed heterotrophic microflora to sources of dissolved organic matter (DOM) typical of its environment and microfloral responses to pulses of DOM.
• 2 Microcosm measurements of dissolved organic carbon (DOC) uptake, dissolved oxygen uptake. ATP concentration and epitluorescence microscopic counts (EMC) were performed using stream-bed sediments and heterogeneous dissolved organic matter (DOM) sources.
• 3 Three study sites included an undisturbed woodlot spring seep, a small stream traversing a cattle pasture and a larger stream draining a catchment used for silage crops, pastures and woodlands.
• 4 The DOM sources were cold water extracts of forest floor leaf litter, bovine manure, the green alga Ulothrix and jewel weed (Impaliens capensis L.) leaves.
• 5 DOC uptake occurring in 2.5–5.0 h incubations indicated an acclimation of the microflora at each site to DOM sources generated by surrounding land use.
• 6 The sediment microflora from the larger stream did not readily metabolize bovine manure DOM and the latter was used in an acclimation experiment.
• 7 A minimum of 48 h of cumulative exposure to bovine manure DOM at 15–20°C were required to yield measurable changes in sediment microbial activity of sediment microbial biomass.
• 8 The same microflora retained an ability to readily metabolize the added DOM source after 72 h of exposure to unamended stream water.
• 9 The time frame of microfloral responses during acclimation indicated that changes leading to the metabolism of a DOM source were initially enzymatic and eventually involved growth and selection for specific decomposers within the microbial community.
• 10 We conclude that in order to utilize naturally occurring pulses of carbon and energy, stream-bed heterotrophs must be already enzymatically prepared, induced, when the pulse occurs.

     

Three-dimensional fluorescence as a tool for investigating the dynamics of dissolved organic matter in the Lake Biwa watershed

Quantitative and qualitative characterizations of dissolved organic matter (DOM) were carried out at the watershed level in central Japan by measuring dissolved organic carbon (DOC) concentration and the three-dimensional excitation–emission matrix (3-D EEM). DOC concentration was low (mean 37 ± 19 µM C) in the upstream waters, whereas, in general, it increased toward the downstream areas (mean 92 ± 47 µM C). Significant variations in DOC concentration were detected among rivers and channels. DOC concentration in the epilimnion of Lake Biwa increased during the summer period and decreased during the winter period. The lake hypolimnion has lower DOC concentration (mean 87 ± 7 µM C) compared with the epilimnion (107 ± 15 µM C). Fulvic acid (FA)-like substances in the DOM were directly characterized by 3-D EEM. The fluorescence peak for upstream DOM was found in regions with longer wavelengths (excitation/emission 386 ± 6/476 ± 5 nm) compared with downstream and lake DOM (351 ± 12/446 ± 15 nm and 341 ± 6/434 ± 6 nm, respectively). The DOC concentration is correlated with fluorescence peak intensity of FA-like substances in DOM in river waters. Such a relationship was not found in lake DOM. A blueshift of the fluorescence peak from upstream to lake DOM was observed. A decrease in fluorescence intensities was also detected during the summer period. These results may suggest that the degradation of FA-like substances in DOM occurs from natural solar irradiation. Protein-like fluorescence was significantly detected in the lake epilimnion during the summer period. A linear relationship between DOC concentration and protein-like fluorescence indicated that an autochthonous input of DOM gave rise to the increase in DOC concentration in the lake epilimnion during the summer. These results may suggest that the 3-D EEM can be used as a tool for the investigation of DOM dynamics at the watershed level with concurrent measurement of DOC concentration and the fluorescence properties of fulvic acid-like and protein-like substances.     

Inter- and intramolecular fluorescence quenching of organic dyes by tryptophan

Steady-state and time-resolved fluorescence measurements were performed to elucidate the fluorescence quenching of oxazine, rhodamine, carbocyanine, and bora-diaza-indacene dyes by amino acids. Among the natural amino acids, tryptophan exhibits the most pronounced quenching efficiency. Especially, the red-absorbing dyes ATTO 655, ATTO 680, and the oxazine derivative MR 121 are strongly quenched almost exclusively by tryptophan due to the formation of weak or nonfluorescent ground-state complexes with association constants, K(ass.), ranging from 96 to 206 M(-1). Rhodamine, fluorescein, and bora-diaza-indacene derivatives that absorb at shorter wavelengths are also quenched substantially by tyrosine residues. The quenching of carbocyanine dyes, such as Cy5, and Alexa 647 by amino acids can be almost neglected. While quenching of ATTO 655, ATTO 680, and the oxazine derivative MR121 by tryptophan is dominated by static quenching, dynamic quenching is more efficient for the two bora-diaza-indacene dyes Bodipy-FL and Bodipy630/650. Labeling of the dyes to tryptophan, tryptophan-containing peptides, and proteins (streptavidin) demonstrates that knowledge of these fluorescence quenching processes is crucial for the development of fluorescence-based diagnostic assays. Changes in the fluorescence quantum yield of dye-labeled peptides and proteins might be used advantageously for the quantification of proteases and specific binding partners.     

Benthic bacterial biomass supported by streamwater dissolved organic matter

Bacterial biomass in surface sediments of a headwater stream was measured as a function of dissolved organic carbon (DOC) flux and temperature. Bacterial biomass was estimated using epifluorescence microscopic counts (EMC) and ATP determinations during exposure to streamwater containing 1,788g DOC/liter and after transfer to groundwater containing 693g DOC/liter. Numbers of bacteria and ATP concentrations averaged 1.36×10⁹ cells and 1,064 ng per gram dry sediment, respectively, under initial DOC exposure. After transfer to low DOC water, biomass estimates dropped by 53 and 55% from EMC and ATP, respectively. The decline to a new steady state occurred within 4 days from ATP assays and within 11 days from EMC measures. A 4°C difference during these exposures had little effect on generation times. The experiment indicated that 27.59 mg/hour of natural DOC supported a steady state bacterial biomass of approximately 10g C/g dry weight of sediment (from EMC determinations). Steady state bacterial biomass estimates on sediments that were previously muffled to remove organic matter were approximately 20-fold lower. The ratio of GTPATP indicated differences in physiological condition or community composition between natural and muffled sediments.     

The application of fluorescence spectroscopy to organic matter characterisation in drinking water treatment

Key to effective disinfection byproduct (DBP) management is source water control and management, and more specifically, organic matter (OM) control and management. However, the content and character of OM in source waters is spatially and temporally variable, and the prediction of its composition is challenging. Water treatment companies require adequate analytical techniques for OM characterisation to maintain the operation of the water supply and treatment systems adjusted to constantly changing environmental conditions. There is a requirement, therefore, for an improved understanding of OM composition and character in source water, how that composition and character varies with flow conditions, and how this impacts on drinking water treatment. This paper demonstrates that fluorescence spectroscopy offers a potential alternative to other analytical methods of OM characterisation. The advantages of fluorescence include rapid, sensitive and selective characterisation of OM, no sample pre-treatment, small sample volume, and the potential for on-line monitoring incorporation. Fluorescence can provide useful information on OM reactivity and treatability together with an indication of the OM sources (allochthonous or autochthonous). The paper discusses a body of literature which has identified relationships between fluorescence spectra and OM physico-chemical properties (i.e. degree of hydrophobicity, microbial content), has applied fluorescence spectroscopy to characterise the changes in OM upon disinfection, and has related the fluorescence properties to DBP formation. Further work is required in the robust management of data arising from fluorescence spectroscopy analysis and, in particular, Excitation Emission Matrices. Consideration must be given as to how the data might best be employed to greatest effect on a routine basis at WTW.     

Introduction of DEAE Sepharose for isolation of dissolved organic matter

Limnology - An anion exchange resin, diethylaminoethyl (DEAE) Sepharose®, was utilized for the isolation of dissolved organic matter (DOM) from fresh waters as an alternative to the...