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.     

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.     

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。     

Net release of dissolved organic matter by the scleractinian coral Acropora pulchra

The net production of dissolved organic matter (DOM) and dissolved combined and free amino acids (DCAA and DFAA, respectively) by the hermatypic coral Acropora pulchra was measured in the submerged condition, and the production rates were normalized to the coral surface area, tissue biomass, and net photosynthetic rates by zooxanthellae. When normalized to the unit surface area, the production rates of dissolved organic carbon and nitrogen (DOC and DON, respectively) were 37 and 4.4 nmol cm^− 2 h^− 1, respectively. Comparing with the photosynthetic rate by zooxanthellae, which was measured by ¹³C-tracer accumulation in the soft tissue of the coral colony, the release rate of DOC corresponded to 5.4% of the daily net photosynthetic production. The tissue biomass of the coral colony was 178 µmol C cm^− 2 and 23 µmol N cm^− 2, indicating that the release of DOC and DON accounted for 0.021% h^− 1 and 0.019% h^− 1 of the tissue C and N, respectively. The C:N ratios of the released DOM (average 8.4) were not significantly different from those of the soft tissue of the coral colonies (average 7.7). While DFAA did almost not accumulate in the incubated seawater, DCAA was considerably released by the coral colonies at the rate of 2.1 nmol cm^− 2 h^− 1 on average. Calculating C and N contents of the hydrolyzable DCAA, it was revealed that about 20% and 50%–60% of the released bulk DOC and DON, respectively, were composed of DCAA.     

Tropical tree species composition affects the oxidation of dissolved organic matter from litter

Plant species effects on soil nutrient availability are relatively well documented, but the effects of species differences in litter chemistry on soil carbon cycling are less well understood, especially in the species-rich tropics. In many wet tropical forest ecosystems, leaching of dissolved organic matter (DOM) from the litter layer accounts for a significant proportion of litter mass loss during decomposition. Here we investigated how tree species differences in soluble dissolved organic C (DOC) and nutrients affected soil CO₂ fluxes in laboratory incubations. We leached DOM from freshly fallen litter of six canopy tree species collected from a tropical rain forest in Costa Rica and measured C-mineralization. We found significant differences in litter solubility and nutrient availability. Following DOM additions to soil, rates of heterotrophic respiration varied by as much as an order of magnitude between species, and overall differences in total soil CO₂ efflux varied by more than four-fold. Variation in the carbon: phosphorus ratio accounted for 51% of the variation in total CO₂ flux between species. These results suggest that tropical tree species composition may influence soil C storage and mineralization via inter-specific variation in plant litter chemistry.     

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。     

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 .     

水溶性有机物在水旱轮作土壤剖面中的分馏现象

水溶性有机物(DOM)是有机物质中最为活跃的组成部分,在陆地生态系统物质的迁移转化过程中起重要作用．通过田间试验和室内理化分析证明了DOM在土壤剖面迁移过程中存在明显的“分馏”现象,随着土层深度的增加,对照、施化肥和施污泥处理土壤DOM的浓度分别由145．8、117．7和114．8mg·kg^-1降到21．57、23．23和13．78mg·kg^-l;不施肥和施化肥处理的土壤DOM随着深度的增加,极性物质所占的比例分别由19．01％和18．47％增至34．97％与44．37％,呈上升趋势,而非极性组分所占比例相应降低;施污泥处理则出现相反的规律,极性组分由36．96％降到17．07％,非极性组分由63．04％增为82．93％．土壤DOM的生物降解率由上到下对照和施化肥处理分别由24．38％和24．00％增大到54．74％和53．81％,而施污泥处理的变化规律则相反,由53．19％降到30．75％．DOM的生物降解率与DOM中极性物质的含量呈正相关关系．紫外光谱进一步证实了这一结果．     

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     

Variations in the composition and adsorption behavior of dissolved organic matter at a small, forested watershed

This study investigated the properties and sorption by goethite of bulk (unfractionated) dissolved organic matter (DOM) from surface and shallow groundwaters at McDonalds Branch, a small freshwater fen in the New Jersey Pine Barrens (USA). Water samples were collected in the spring and fall seasons from two surface-water sampling sites, an upstream potential recharge area and a downstream discharge area, as well as from a set of in-stream nested wells in the upstream potential recharge area. Changes in DOM concentration, molecular weight distribution, and molar absorptivity at 280 nm were measured. Surface and shallow (1.6 m below land surface) groundwater samples collected in spring 1997 in the potential recharge zone (actual recharge impeded by an extensive clay lens) were found to be very similar in terms of DOM concentrations and physicochemical properties and is believe to originate from a common source. Samples taken in fall 1997 yielded no surface water because of drought conditions, and the shallow groundwater DOM collected from the recharge well contained significantly less and chemically altered DOM. This change in chemical properties is believed to be caused in part by fractionation resulting from sorption to mineral phases. Batch isotherm experiments show that sorption by goethite of the DOM from both spring surface and shallow groundwaters in the potential recharge area were similar, whereas the fall groundwater possessed a much lower affinity for the sorbent. This study demonstrated that shallow groundwaters collected under different climatic and hydrologic conditions (spring, high flow versus fall, drought conditions) resulted in different physicochemical properties and adsorption affinities.     

Particulate and dissolved organic matter in a small partly forested Ontario stream

Weekly measurements during the open season at five stations on a small Ontario stream system showed that the size distribution of fine particles in the water varied irregularly. In general, rainfall increased their total amount and also the concentration of dissolved organic carbon. Clearly other local factors affect the supply of particles, and each reach behaves individually and may react differently to successive storms. The behaviour of dissolved material is more predictable, and it is clear that much is rapidly removed from solution. It was shown that high concentrations of particles are associated with high amounts of plant pigments, carbohydrate, and protein. Similarly dissolved carbohydrate and protein are raised when rain increases dissolved organic carbon. These findings suggest a series of mechanisms by which a woodland stream may trap woodland produced energy and cycle it through the aquatic system.This work was supported by a research grant from the National Research Council of Canada to H. B. N. Hynes.     

Stream dissolved organic matter bioavailability and composition in watersheds underlain with discontinuous permafrost

We examined the impact of permafrost on dissolved organic matter (DOM) composition in Caribou-Poker Creeks Research Watershed (CPCRW), a watershed underlain with discontinuous permafrost, in interior Alaska. We analyzed long term data from watersheds underlain with varying degrees of permafrost, sampled springs and thermokarsts, used fluorescence spectroscopy, and measured the bioavailabity of dissolved organic carbon (DOC). Permafrost driven patterns in hydrology and vegetation influenced DOM patterns in streams, with the stream draining the high permafrost watershed having higher DOC and dissolved organic nitrogen (DON) concentrations, higher DOC:DON and greater specific ultraviolet absorbance (SUVA) than the streams draining the low and medium permafrost watersheds. Streams, springs and thermokarsts exhibited a wide range of DOC and DON concentrations (1.5–37.5 mgC/L and 0.14–1.26 mgN/L, respectively), DOC:DON (7.1–42.8) and SUVA (1.5–4.7 L mgC⁻¹ m⁻¹). All sites had a high proportion of humic components, a low proportion of protein components, and a low fluorescence index value (1.3–1.4), generally consistent with terrestrially derived DOM. Principal component analysis revealed distinct groups in our fluorescence data determined by diagenetic processing and DOM source. The proportion of bioavailable DOC ranged from 2 to 35%, with the proportion of tyrosine- and tryptophan-like fluorophores in the DOM being a major predictor of DOC loss (p < 0.05, R ² = 0.99). Our results indicate that the degradation of permafrost in CPCRW will result in a decrease in DOC and DON concentrations, a decline in DOC:DON, and a reduction in SUVA, possibly accompanied by a change in the proportion of bioavailable DOC.     

Spectroscopic characterization and molecular weight distribution of dissolved organic matter in sediment porewaters from Lake Erhai, Southwest China

Dissolved organic matter (DOM) in sediment porewaters from Lake Erhai, Southwest China was investigated using dissolved organic carbon (DOC) concentration, UV absorbance, fluorescence and molecular weight distribution. DOC exhibited a high concentration at the sediment–water interface with a rapid decrease to the oxic–anoxic interface at approximately 7 cm, and then increased with depth. Similar trends were also found for the UV absorption coefficients at 254 and 280 nm in the porewaters. DNA in the sediment was also measured, which confirmed the high abundance of aerobic bacteria in the upper layer of the sediment. Both humic-like (peaks A and C) and protein-like (peaks B and D) fluorescence were observed in the porewater DOM, and their fluorescence intensities exhibited a similar porewater profile as DOC concentration. A strong correlation was found between the peak fluorescence intensity ratio r(A, C) and r(D, B). Both the fluorescence index and UV absorption coefficient at 254 nm suggested a dramatic increase in aromaticity of porewater DOM across the oxic–anoxic interface. Porewater DOM exhibited a multimodal distribution of molecular weight with a relatively low polydispersity. The results of this study offer significant insight into the nature and properties of DOM in freshwater ecosystems.     

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

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

海水中天然细菌对不同生源要素有机物的矿化作用

海洋异养细菌是微食物网中非常重要的一部分,它消耗海洋中的溶解有机物并进行细菌的二次生产。细菌对不同种类的溶解有机物分解速率不同,并且有机物的生物利用率影响细菌的生长。研究了含有不同生源要素的4种溶解有机物(DOM)在海洋异养细菌存在下的矿化作用及对细菌生长的影响。结果表明:添加不同生源要素的有机物,对海洋天然异养细菌的生长均有促进作用,其比生长速率(μ)的大小顺序为:NCPS对照组,说明含氮有机物更有助于细菌的生长;细菌生长效率(BGE)的大小顺序为:对照组CPNS,说明细菌的二次生产跟有机物的分解速率没有直接相关性;单个细菌对有机物的消耗速率I为:NCPS对照组,说明细菌生长速率与有机物消耗速率直接相关;有机物的生物可利用性顺序为:NCPS对照组,与有机物的消耗速率顺序一致。上述结果表明,具有相同结构但不同生源要素的有机物的矿化速率存在差异,含氮有机物最容易分解,其次是含碳有机物,然后是含磷有机物,含硫有机物分解最慢,说明细菌对含有不同生源要素有机物的分解利用存在差异。     

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.     

Crop residue-derived dissolved organic matter accelerates the decomposition of native soil organic carbon in a temperate agricultural ecosystem

Crop residue-derived dissolved organic matter (DOM) plays an important role in soil carbon (C) cycling. To investigate the effects of maize residue-derived DOM and urea additions on the native soil organic carbon (SOC) decomposition and soil net C balance a pot experiment was carried out during the winter wheat growing season in the North China Plain (NCP). The results showed that adding maize residue-derived DOM alone (RDOM) or together with urea (RDOM?+?N) accelerated the decomposition of native SOC and resulted in a net SOC loss. The net loss of SOC was 3.90?±?0.61 and 3.53?±?0.48?g?C?m^?2 in RDOM and RDOM?+?N treatments, respectively. The stimulatory effect of per unit DOM-C addition on the native SOC decomposition was 0.25?±?0.05 and 0.45?±?0.07 for the RDOM and RDOM?+?N treatments, respectively. Increases in the microbial biomass and the activity of β-glucosidase, invertase and cellobiohydrolase as well as soil mineral N content were responsible for a more intense priming effect in DOM-amended soils. The positive relationship between primed soil C and soil available N (R?=?0.76, P?<?0.05) suggested that the stimulation of decomposition of native SOC by DOM addition would be enhanced by nitrogen fertilizer application.     

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.     

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.