Impact of Dissolved Organic Matter on the Desorption and Mineralization Rates of Naphthalene

The persistence of organic contaminants in plant-soil systems will be largely determined by the basic processes controlling bioavailability: desorption and biodegradation. Both processes can be affected by the presence of and variations in dissolved organic matter (DOM). To evaluate potential effects of DOM in surface soil remediation systems, the kinetics of naphthalene desorption from soil and mineralization in soil solution in the presence of DOM were studied in completely mixed batch reactors (CMBRs). Three different DOM solutions were studied. These were obtained from water extraction of two different soils (muck-highly organic and alfalfa field-agricultural) and a third prepared by reconstituting a fulvic acid reference standard purchased commercially. Neither the desorption rate nor equilibrium partitioning of naphthalene was affected by the presence of varying DOM solutions. The effect on mineralization was evaluated based on an evaluation of a first-order rate constant produced by nonlinear regression of data fitted to a ¹⁴CO₂ production model. For the muck DOM solution, alfalfa DOM solution, and fulvic acid DOM solution, first-order rate constants were 0.0474, 0.0657, 0.0422 min_?1, respectively. Using uncertainty analysis, these differences were found not to be significant at a 90% confidence level. Although not apparent in this data, the impact of DOM on the mechanisms of desorption and biodegradation in a plant -soil environment may be important for other contaminant/organism/soil combinations. With the increased interest in phytoremediation and land farming as means of treating organic contaminants, further investigation of such interactions may be warranted.     

Use of electrospray ionization (ESI) mass spectrometry to investigate complex dissolved organic matter (DOM) and its potential applications in phytoplankton research

Organic nutrients are one of many factors considered to be important in the growth and proliferation of phytoplankton including many species that cause harmful algal blooms (HABs). Several studies have investigated the effects of known organic compounds on phytoplankton growth, however, the role of natural dissolved organic matter (DOM) in phytoplankton nutrition remains understudied at the compound level. This lack of research is due in part to analytical limitations for the characterization of DOM compounds. Electrospray ionization (ESI) mass spectrometry (MS) provides an unprecedented level of chemical information on thousands of organic compounds that comprise the bulk DOM pool. In this paper we provide a brief overview of some of the benefits and caveats of using ESI to investigate DOM in natural freshwater and marine systems and show an example of ESI-MS DOM characterization for a natural bloom of the raphidophyte Chattonella cf. verruculosa.     

Temperature Dependence of Photodegradation of Dissolved Organic Matter to Dissolved Inorganic Carbon and Particulate Organic Carbon

Photochemical transformation of dissolved organic matter (DOM) has been studied for more than two decades. Usually, laboratory or “in-situ” experiments are used to determine photodegradation variables. A common problem with these experiments is that the photodegradation experiments are done at higher than ambient temperature. Five laboratory experiments were done to determine the effect of temperature on photochemical degradation of DOM. Experimental results showed strong dependence of photodegradation on temperature. Mathematical modeling of processes revealed that two different pathways engaged in photochemical transformation of DOM to dissolved inorganic carbon (DIC) strongly depend on temperature. Direct oxidation of DOM to DIC dominated at low temperatures while conversion of DOM to intermediate particulate organic carbon (POC) prior to oxidation to DIC dominated at high temperatures. It is necessary to consider this strong dependence when the results of laboratory experiments are interpreted in regard to natural processes. Photodegradation experiments done at higher than ambient temperature will necessitate correction of rate constants.     

Molecular weight fractionation of dissolved organic matter (DOM) released by phytoplankton

The application of an ultrafiltration procedure for fractionation of molecular weight of dissolved organic matter (DOM) extracellularly released by phytoplankton is described. Seven ultrafiltration membranes Diaflo (Amicon Corp. USA), with range 500--300,000 molecular weight (MW), were used for separation of different molecular weight compounds released by phytoplankton in Rhode River estuary of Chesapeake Bay, and their composition was determined. Percentage of extracellular release of DOM by phytoplankton varied from 3.92--68.07% of total carbon fixed in photosynthesis. The composition of algal extracellular products varied with different phytoplankton populations. However, two fractions of molecular weight compounds dominated in the composition of DOM released, i.e. a low molecular weight fraction of less than 1,000 MW and the fraction between 10,000--30,000 MW. The ultrafiltration procedure is effective for studying the composition of DOM released by phytoplankton in natural waters.     

A large molecular size fraction of riverine high molecular weight dissolved organic matter (HMW DOM) stimulates growth of the harmful dinoflagellate Alexandrium minutum

An increase in the concentration of riverine dissolved organic matter (DOM) has been observed during the last decades, and this material can stimulate marine plankton in coastal waters with significant freshwater input. We studied the effect of two size fractions of riverine high molecular weight dissolved organic matter (HMW DOM), isolated with tangential ultrafiltration, on the harmful dinoflagellate Alexandrium minutum and a natural isolate of marine bacteria under laboratory conditions. Both A. minutum and bacteria grew significantly better with the low MW DOM compared to both the high MW DOM fraction and controls (no DOM additions). This experiment demonstrates that the harmful algae A. minutum and bacteria benefit from larger molecules of river HMW DOM, and highlights the potential of A. minutum to utilize organic nitrogen from large DOM molecules. This ability may enhance their likelihood of success in estuaries/costal waters with a humic rich freshwater input, especially when the relative amount of large molecules within DOM is more pronounced.     

Evidence for key enzymatic controls on metabolism of Arctic river organic matter

Permafrost thaw in the Arctic driven by climate change is mobilizing ancient terrigenous organic carbon (OC) into fluvial networks. Understanding the controls on metabolism of this OC is imperative for assessing its role with respect to climate feedbacks. In this study, we examined the effect of inorganic nutrient supply and dissolved organic matter (DOM) composition on aquatic extracellular enzyme activities (EEAs) in waters draining the Kolyma River Basin (Siberia), including permafrost‐derived OC. Reducing the phenolic content of the DOM pool resulted in dramatic increases in hydrolase EEAs (e.g., phosphatase activity increased >28‐fold) supporting the idea that high concentrations of polyphenolic compounds in DOM (e.g., plant structural tissues) inhibit enzyme synthesis or activity, limiting OC degradation. EEAs were significantly more responsive to inorganic nutrient additions only after phenolic inhibition was experimentally removed. In controlled mixtures of modern OC and thawed permafrost endmember OC sources, respiration rates per unit dissolved OC were 1.3–1.6 times higher in waters containing ancient carbon, suggesting that permafrost‐derived OC was more available for microbial mineralization. In addition, waters containing ancient permafrost‐derived OC supported elevated phosphatase and glucosidase activities. Based on these combined results, we propose that both composition and nutrient availability regulate DOM metabolism in Arctic aquatic ecosystems. Our empirical findings are incorporated into a mechanistic conceptual model highlighting two key enzymatic processes in the mineralization of riverine OM: (i) the role of phenol oxidase activity in reducing inhibitory phenolic compounds and (ii) the role of phosphatase in mobilizing organic P. Permafrost‐derived DOM degradation was less constrained by this initial ‘phenolic‐OM’ inhibition; thus, informing reports of high biological availability of ancient, permafrost‐derived DOM with clear ramifications for its metabolism in fluvial networks and feedbacks to climate.     

亚热带米槠林不同更新方式对土壤可溶性有机质降解性的影响

可溶性有机质(DOM)的生物降解性影响着土壤有机质的存留和释放,对深入认识森林土壤养分循环意义重大。为探究森林更新对土壤DOM降解特征的影响,选取亚热带地区米槠天然林(NF)、米槠次生林(SF)和米槠人工促进天然更新林(AR)土壤DOM溶液为研究对象,进行室内降解(42 d)试验。结果表明: 1)3种林分土壤可溶性有机碳(DOC)的降解率和易降解DOC的比例均为SF>AR>NF;可溶性有机氮(DON)和微生物生物量碳(MBC)是显著影响易降解DOC比例的因子;2)难降解组分占3种林分土壤DOC的大部分(72.3%～94.6%),其周转时间长,有利于稳定土壤有机质(SOC)的形成;3)土壤DOM最初的腐殖化指数(HIX_em)会影响易降解DOC的周转时间。DOM光谱结构随降解过程呈现动态变化,说明DOM中易降解组分被消耗完后,微生物会转而降解芳香类和疏水性物质以获取碳源。综上,米槠天然林更新为次生林和人促林后增加了易降解DOC的比例,提高了土壤DOM生物可降解性,不利于SOC的积累。     

Effects of Dissolved Organic Matter Photoproducts and Mineral Nutrient Supply on Bacterial Growth in Mediterranean Inland Waters

Sunlight reacts with dissolved organic matter (DOM) modifying its availability as bacterial substrate. We assessed the impact of DOM photoproducts and mineral nutrient supply on bacterial growth in seven inland waters from the South of Spain, where DOM is characterized by low chromophoric content and long residence time. Factorial experiments were performed with presence vs absence of DOM photoproducts and mineral nutrient supply. In six of the seven experiments, we found a significant and negative effect of DOM photoproducts on bacterial growth and a significant and positive effect of mineral nutrient supply. The interaction of these two factors leaded to a compensation of negative effects of photoproducts by availability of mineral nutrients. Dissolved organic matter diagenetic status and the ionic environment where organic carbon is dissolved can be influencing bacterial DOM processing.     

Impact of iron-complex (Fe(III)-NTA) on photoinduced degradation of 4-chlorophenol in aqueous solution.

In this research work, the photochemical impact of Fe(III)-nitrilotriacetic acid complex (FeNTA) on the fate of an organic pollutant (4-chlorophenol (4-CP)) was investigated in natural waters. The quantum yields of the photodecomposition of the FeNTA complex and of Fe(II) formation, by an intra-molecular photoredox process (the first stage of the reaction) are high. This photoredox reaction represents the first step of the process leading to 4-CP disappearance. Whereas oxygen does not affect FeNTA photodegradation, 4-CP depletion requires the presence of oxygen. The radical species HO and CO3*- responsible of the degradation were identified by ESR spectroscopy under irradiation. Two different wavelength-dependent mechanisms of 4-chlorophenol degradation are proposed. It clearly appears that under solar irradiation, iron organic complexes like FeNTA can play a significant role on the fate of the organic compounds present in natural waters.     

Effects of dissolved organic matter (DOM) at environmentally relevant carbon concentrations on atrazine degradation by Chelatobacter heintzii SalB

The dissolved organic matter (DOM) is the term used for organic components of natural origin present in the soil solution and is probably the most available C-source that primes microbial activity in subsoils. Contrasting effects of organic C components on pesticide degradation have been reported; however, most studies have used model organic compounds with compositions and concentrations which differ substantially from those found in the environment. Degradation of atrazine (AT) by Chelatobacter heintzii SalB was monitored in liquid batch assays in the absence or presence of well-defined model C compounds (glucose, gluconate and citrate) as model DOM (mDOM) or complex, less-defined, environmental DOM solutions (eDOM: isolated humic substances, soil and plant residue extracts) at environmentally relevant concentrations. Glucose significantly increased AT degradation rate by more than a factor of 8 at and above 2.5?mg C L(?-?1). Optical density measurements showed that this stimulation is related to microbial growth. Gluconate and citrate had no effects unless at non-relevant concentrations (1,000?mg DOC L(?-?1)) at which stimulations (gluconate) or inhibitions (citrate) were found. The effects of eDOM added at 10?mg DOC L(?-?1) on AT degradation were generally small. The AT degradation time was reduced by factors 1.4-1.9 in the presence of humic acids and eDOM from soils amended with plant residues; however, no effects were found for fulvic acids or eDOM from a soil leachate solution or extracted from unamended peat or forest soil. In conclusion, DOM supplied as both mDOM and eDOM did not inhibit AT degradation at environmentally relevant concentrations, and stimulation can be found for selected DOM samples and this is partly related to its effect on growth.     

Seasonal and spatial variability of dissolved organic matter composition in the lower Amazon River

We analyzed the molecular composition of dissolved organic matter (DOM) in the lower Amazon River (ca. 850 km from Óbidos to the mouth) using ultrahigh-resolution mass spectrometry and geochemical tracers. Changes in DOM composition along this lower reach suggest a transition from higher plant-derived DOM to more algal/microbial-derived DOM. This result was likely due to a combination of autochthonous production, alteration of terrigenous DOM as it transits down the river, and increased algal inputs from floodplain lakes and clearwater tributaries during high discharge conditions. Spatial gradients in dissolved organic carbon (DOC) concentrations varied with discharge. Maximal DOC concentrations were observed near the mouth during high water, highlighting the importance of lateral inputs of DOM along the lower river. The majority of DOM molecular formulae did not change within the time it takes the water in the mainstem to be transported through the lower reach. This is indicative of molecules representing a mixture of compounds that are resistant to rapid alteration and reactive compounds that are continuously replenished by the lateral input of terrestrial organic matter from the landscape, tributaries, and floodplains. River water incubations revealed that photo- and bio-transformation alter at most 30% of the DOM molecular formulae. River discharge at the mouth differed from the sum of discharge measurements made at Óbidos and the main gauged tributaries in the lower Amazon. This indicates that changes in hydrology and associated variations in the source waters along the lower reach affected the molecular composition of the DOM that is being transported from the Amazon River to the coastal ocean.     

Ammonia-oxidizing archaea release a suite of organic compounds potentially fueling prokaryotic heterotrophy in the ocean

Ammonia-oxidizing archaea (AOA) constitute a considerable fraction of microbial biomass in the global ocean, comprising 20%–40% of the ocean's prokaryotic plankton. However, it remains enigmatic to what extent these chemolithoautotrophic archaea release dissolved organic carbon (DOC). A combination of targeted and untargeted metabolomics was used to characterize the exometabolomes of three model AOA strains of the Nitrosopumilus genus. Our results indicate that marine AOA exude a suite of organic compounds with potentially varying reactivities, dominated by nitrogen-containing compounds. A significant fraction of the released dissolved organic matter (DOM) consists of labile compounds, which typically limit prokaryotic heterotrophic activity in open ocean waters, including amino acids, thymidine and B vitamins. Amino acid release rates corresponded with ammonia oxidation activity and the three Nitrosopumilus strains predominantly released hydrophobic amino acids, potentially as a result of passive diffusion. Despite the low contribution of DOC released by AOA (~0.08%–1.05%) to the heterotrophic prokaryotic carbon demand, the release of physiologically relevant metabolites could be crucial for microbes that are auxotrophic for some of these compounds, including members of the globally abundant and ubiquitous SAR11 clade.     

Organic biogeochemistry of groundwater at a mountain coal mine

Measurements of dissolved organic matter (DOM), humic and fulvic acids, carbohydrates, tannins + lignins, phenols and amino acids were made in the groundwater permeating Reclamation site 2 at the Canmore Coal Mine (Alberta, Canada). Estimates of the number of bacteria present in the groundwater were also made using plate and direct count techniques. Temperature, pH, Eh, and oxygen content of the groundwater were measured on two occasions. DOM was very low in concentration (av. 1.62 mg/liter) and consisted principally of fulvic acid. Humic acids formed about 20% of DOM, carbohydrates 6%, tannins + lignins 4%, and trace compounds (phenols, amino acids, and proteins) 2%. Seasonal variations were observed, with tannins + lignins and carbohydrates reaching their highest concentration in the summer, and humic and fulvic acids, and DOM peaking in the winter. The organic composition of the groundwater upstream of the reclamation site did not differ significantly from groundwater sampled from within the reclamation site. Differences were observed, however, between ground and surface waters draining the site. No correlation between concentration and depth was observed. Large numbers of bacteria were found in groundwater using both plate count and direct count methods. Populations were only modestly correlated with the concentrations of organic compounds (r<0.9). Heterotrophic bacteria must have been dependent upon organic matter (both as DOM and as insoluble organic matter in the spoil) for growth, however. The groundwater bacteria studied appeared to be characterized by slow growth under adverse geological conditions with only low concentrations of labile organic compounds present.     

Uptake of Dissolved Organic Carbon by Gammaproteobacterial Subgroups in Coastal Waters of the West Antarctic Peninsula

Heterotrophic bacteria are well known to be key players in the turnover of dissolved organic material (DOM) in the oceans, but the relationship between DOM uptake and bacterial clades is still not well understood. Here we explore the turnover and single-cell use of glucose, an amino acid mixture, N-acetylglucosamine (NAG), and protein by gammaproteobacterial clades in coastal waters of the West Antarctic Peninsula in summer and fall. More than 60% of the cells within two closely related gammaproteobacterial clades, Ant4D3 and Arctic96B-16, were active in using the amino acid mixture, protein, and NAG. In contrast, an average of only 7% of all SAR86 cells used amino acids and protein even in summer when DOM use was high. In addition to DOM uptake within a group, we explored the contribution of the three gammaproteobacterial groups to total community uptake of a compound. SAR86 contributed 5- to 10-fold less than the other gammaproteobacterial subgroups to the uptake of all compounds. We found that the overall contribution of the Ant4D3 clade to DOM uptake was highest, whereas the SAR86 clade contributed the least to DOM turnover in West Antarctic Peninsula waters. Our results suggest that the low growth activity of a bacterial clade leads to low abundance, fewer active cells and a low contribution to the turnover of DOM components.     

Effective isolation of bacterioplankton genus Polynucleobacter from freshwater environments grown on photochemically degraded dissolved organic matter

Effective isolation of freshwater bacterioplankton belonging to genus Polynucleobacter from a shallow eutrophic lake and its tributary was achieved by size-selective filtration with a 0.7-μm pore filter and cultivation on R2A agar medium. Partial 16S rRNA gene analysis showed that over 80% of all the strains were highly similar to the Polynucleobacter cluster. Essential medium components for effective cultivation are pyruvate, yeast extract and peptone, whereas soluble starch and glucose are not necessary. Isolate KF001 (affiliated with Polynucleobacter subcluster D) has a strict requirement for organic acids as carbon sources, and we hypothesize that the Polynucleobacter cluster of bacteria could utilize compounds formed via photochemically dissolved organic matter (DOM) degradation for growth. Because organic acids form from solar radiation of DOM in aquatic environments, carbon sources that are typical products of DOM photochemical degradation were added to the medium. These compounds were readily utilized by KF001 in this study. Finally, we observed the stimulation of strain KF001 activity by photochemical degradation of natural lake water. Our findings suggest a carbon flow of DOM photoproducts to Polynucleobacter in the freshwater microbial loop.     

土壤溶解性有机质及其表面反应性的研究进展

溶解性有机质(DOM)是土壤溶液中的一个重要的组成部分,在土壤化学和生物过程中起着十分重要的作用。虽然DOM在天然有机质中所占的比例并不高,但它将土壤中的矿物质、有机质联系在一起,并能调控环境污染物的迁移转化与归宿,因此国内外学者都很重视溶解性有机质对土壤环境中污染物环境行为影响的研究。综述了DOM的分类和分离技术,DOM的结构及其表征方法,DOM的表面反应性以及对有机污染物、重金属在土壤中吸附、迁移的影响等,并提出了有待于进一步研究的一些问题。     

Strong coupling between natural Planctomycetes and changes in the quality of dissolved organic matter in freshwater samples

Dilution-regrowth experiments coupled to fluorescence in situ hybridization were conducted with samples from two humic reservoirs in order to examine how inorganic nutrients (N, P) affect free-living bacterioplankton phylogenetic groups and subsequently the quality of dissolved organic matter (DOM). The experiments were complemented by analyses of the empirical relationships between the targeted bacteria, nutrients, DOM and grazers. The ratio of absorbance of waters (A) at 250 and 365 nm (A(250 nm):A(365 nm)), which has been found to increase with the proportion of small molecules in the DOM pool in other humic waters, was used as an index of DOM quality. When nutrient stimulated bacteria, both the responses of bacterial groups (in the absence of grazers) and the ratio A(250 nm):A(365 nm) were generally different between treatments (+N, +P, +NP), suggesting that in nutrient-poor systems, differences in the type of inorganic nutrient supply will ultimately cause differences in DOM quality. The ratio A(250 nm),:A(365 nm) peaked in the +N treatments where members of the Planctomycetes (PLA) were the most stimulated group, and across treatments, PLA best explained (positive relationship) variations in this ratio. Consistent with this, the in situ data showed that the removal of the negative effects of flagellates on PLA yielded the highest R(2) in attempts to use bacterial groups to explain variations in A(250 nm):A(365 nm). These findings provide lines of evidence, not previously demonstrated in natural waters, that Planctomycetes may be an important factor changing the DOM quality, particularly in nutrient-poor systems when supplied with inorganic N.     

Contrasting effects of solar UV radiation on dissolved organic sources for bacterial growth

The photochemical transformation of dissolved organic matter (DOM) in lakes and oceans has been shown to either reduce or enhance bacterial utilization. We compared the effects of UV radiation on the bacterial use of DOM in a wide range of lakes. Although complex DOM was converted in all irradiated samples into carboxylic acids that are readily utilized by bacteria, irradiation in several lakes resulted in a decreased ability of DOM to support bacterial growth. The effect of irradiation on the ability of DOM to promote bacterial growth was a positive function of the terrestrial humic matter, and a negative function of indigenous algal production. We suggest that the net effect of irradiation is a result of counteracting but concurrent processes rendering DOM either labile or recalcitrant. Humic DOM is predominantly transformed into forms of increased lability, whereas photochemical transformation into compounds of decreased bacterial substrate quality dominates in algal-derived DOM. Hence, solar-induced photochemical reactions interact with microbial degraders in different ways, depending on the origin and nature of the organic matter, affecting the transfer of energy within aquatic food webs, as well as the degradation and preservation of detrital organic matter, in different directions.     

The role of dissolved organic matter bioavailability in promoting phytoplankton blooms in Florida Bay

The clear, shallow, oligotrophic waters of Florida Bay are characterized by low phytoplankton biomass, yet periodic cyanobacteria and diatom blooms do occur. We hypothesized that allochthonous dissolved organic matter (DOM) was providing a subsidy to the system in the form of bound nutrients. Water from four bay sites was incubated under natural light and dark conditions with enrichments of either DOM ( > 1 kD, 2×DOM) or inorganic nutrients (N+P). Samples were analyzed for bacterial numbers, bacterial production, phytoplankton biomass, phytoplankton community structure, and production, nutrients, and alkaline phosphatase (AP) activity. The influence of 2×DOM enrichment on phytoplankton biomass developed slowly during the incubations and was relatively small compared to nutrient additions. Inorganic nutrient additions resulted in an ephemeral bloom characterized initially as cyanobacterial and brown algae but which changed to dinoflagellate and/or brown algae by day six. The DIN:TP ratio decreased 10-fold in the N+P treatments as the system progressed towards N limitation. This ratio did not change significantly for 2×DOM treatments. In addition, these experiments indicated that both autotrophic and heterotrophic microbial populations in Florida Bay may fluctuate in their limitation by organic and inorganic nutrient availability. Both N+P and 2×DOM enrichments revealed significant and positive response in bioavailability of dissolved organic carbon (BDOC). Potential BDOC ranged from 1.1 to 35.5%, with the most labile forms occurring in Whipray Basin. BDOC at all sites was stimulated by the 2×DOM addition. Except for Duck Key, BDOC at all sites was also stimulated by the addition of N+P. BDOC was lower in the dry season than in the wet season (5.56% vs. 16.86%). This may be explained by the distinct chemical characteristics of the DOM produced at different times of year. Thus, both the heterotrophic and autotrophic microbial communities in Florida Bay are modulated by bioavailability of DOM. This has ramifications for the fate of DOM from the Everglades inputs, implicating DOM bioavailability as a contributing factor in regulating the onset, persistence, and composition of phytoplankton blooms.