Molecular Weight Dissolved Organic Matter Research Articles

Photochemical reactivities of dissolved organic matter (DOM) in a sub-alpine lake revealed by EEM-PARAFAC: An insight into the fate of allochthonous DOM in alpine lakes affected by climate change

Due to climate change, tree line advance is occurring in many alpine regions. Within the next 50 to 100years, alpine lake catchments are expected to develop increased vegetation cover similar to that of sub-alpine lake catchments which currently exist below the tree line. Such changes in vegetation could trigger increased allochthonous DOM inputs to alpine lakes. To understand the fate of allochthonous DOM in alpine lakes impacted by climate change, the photochemical reactivity of DOM in sub-alpine Lake Tiancai (located 200m below the tree line) was investigated by excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) and UV–Vis spectra analysis. With photo-exposure, a decrease in apparent DOM molecular weight was observed and 32% DOM was photomineralized to CO2. Interestingly, the aromaticity of DOM increased after photodegradation, as evidenced by increases in both the specific UV absorbance at 254nm (SUVA254) and the humification index (HIX). Five EEM-PARAFAC components were identified, including four terrestrially-derived substances (C1, C2, C3 and C4; allochthonous) and one tryptophan-like substance (C5; autochthonous). Generally, allochthonous DOM represented by C2 and C3 exhibited greater photoreactivity than autochthonous DOM represented by C5. C4 was identified as a possible photoproduct with relatively high aromaticity and photorefractive tendencies and contributed to the observed increase in SUVA254 and HIX. UV light facilitated the photodegradation of DOM and had the greatest effect on the removal of C3. This study provides information on the transformation of EEM-PARAFAC components in a sub-alpine lake, which is important in understanding the fate of increased allochthonous DOM inputs to alpine lakes impacted by climate change.

Mixing and photoreactivity of dissolved organic matter in the Nelson/Hayes estuarine system (Hudson Bay, Canada)

This work presents the results of a 4-year study (2009–2012) investigating the mixing and photoreactivity of dissolved organic matter (DOM) in the Nelson/Hayes estuary (Hudson Bay). Dissolved organic carbon (DOC), colored DOM, and humic-like DOM decreased with increasing salinity (r2=0.70–0.84). Removal of DOM was noticeable at low to mid salinity range, likely due to degradation and/or adsorption to particles. DOM photobleaching rates (i.e., decrease in DOM signal resulting from exposure to solar radiation) ranged from 0.005 to 0.030h−1, corresponding to half-lives of 4.9–9.9days. Dissolved organic matter from the Nelson and Hayes Rivers was more photoreactive than from the estuary where the photodegradation of terrestrial DOM decreased with increasing salinity. Coincident with the loss of CDOM absorption was an increase in spectral slope S, suggesting a decrease in DOM molecular weight. Marked differences in photoreactivity of protein- and humic-like DOM were observed with highly humidified material being the most photosensitive. Information generated by our study will provide a valuable data set for better understanding the impacts of future hydroelectric development and climate change on DOM biogeochemical dynamics in the Nelson/Hayes estuary and coastal domain. This study will constitute a reference on terrestrial DOM fate prior to building additional generating capacity on the Nelson River.

Molecular characterization of low molecular weight dissolved organic matter in water reclamation processes using Orbitrap mass spectrometry

Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by “unknown” screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m/z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation.

High-performance size exclusion chromatography with a multi-wavelength absorbance detector study on dissolved organic matter characterisation along a water distribution system

This study examined the associations between dissolved organic matter (DOM) characteristics and potential nitrification occurrence in the presence of chloramine along a drinking water distribution system. High-performance size exclusion chromatography (HPSEC) coupled with a multiple wavelength detector (200–280nm) was employed to characterise DOM by molecular weight distribution, bacterial activity was analysed using flow cytometry, and a package of simple analytical tools, such as dissolved organic carbon, absorbance at 254nm, nitrate, nitrite, ammonia and total disinfectant residual were also applied and their applicability to indicate water quality changes in distribution systems were also evaluated. Results showed that multi-wavelength HPSEC analysis was useful to provide information about DOM character while changes in molecule weight profiles at wavelengths less than 230nm were also able to be related to other water quality parameters. Correct selection of the UV wavelengths can be an important factor for providing appropriate indicators associated with different DOM compositions. DOM molecular weight in the range of 0.2–0.5kDa measured at 210nm correlated positively with oxidised nitrogen concentration (r=0.99), and the concentrations of active bacterial cells in the distribution system (r=0.85). Our study also showed that the changes of DOM character and bacterial cells were significant in those sampling points that had decreases in total disinfectant residual. HPSEC-UV measured at 210nm and flow cytometry can detect the changes of low molecular weight of DOM and bacterial levels, respectively, when nitrification occurred within the chloraminated distribution system.

Transport and transformation of dissolved organic matter in the Neuse River estuarine system, NC, USA, following Hurricane Irene (2011)

Rivers are major conduits for the transport of allochthonous dissolved organic matter (DOM) to the ocean in coupled land–coastal systems. DOM can regulate biogeochemical processes and affect water quality, depending on the concentration and quality of DOM. By using spectral parameters calculated from chromophoric dissolved organic matter (CDOM) ultraviolet-visible absorption spectra, along with dissolved organic carbon (DOC) concentrations, we examined the input and change in the amount and quality of DOM in surface waters of the lower Neuse River and upper–middle regions of the Neuse Estuary following a major rainfall (30cm in 1 day) associated with Hurricane Irene (2011). CDOM and DOC nearly tripled in the 3 days following the storm. Although a strong linear relationship was observed between DOC and CDOM absorption coefficient at 350nm (R2=0.85), a higher fraction of non-chromophoric DOC to CDOM was observed during the rising river discharge. The spectral slope at 275–295nm and the slope ratio (275–295:350–400nm) indicated a shift from higher to lower molecular-weight DOM as it transited through the estuary, probably as a result of photodegradation. The present study demonstrated the utility of using CDOM spectral parameters for examining the flux and transformation of DOM in coastal waters following major rain events.

Effects of nitrate and phosphate supply on chromophoric and fluorescent dissolved organic matter in the Eastern Tropical North Atlantic: a mesocosm study

Abstract. In open-ocean regions, as is the Eastern Tropical North Atlantic (ETNA), pelagic production is the main source of dissolved organic matter (DOM) and is affected by dissolved inorganic nitrogen (DIN) and phosphorus (DIP) concentrations. Changes in pelagic production under nutrient amendments were shown to also modify DOM quantity and quality. However, little information is available about the effects of nutrient variability on chromophoric (CDOM) and fluorescent (FDOM) DOM dynamics. Here we present results from two mesocosm experiments ("Varied P" and "Varied N") conducted with a natural plankton community from the ETNA, where the effects of DIP and DIN supply on DOM optical properties were studied. CDOM accumulated proportionally to phytoplankton biomass during the experiments. Spectral slope (S) decreased over time indicating accumulation of high molecular weight DOM. In Varied N, an additional CDOM portion, as a result of bacterial DOM reworking, was determined. It increased the CDOM fraction in DOC proportionally to the supplied DIN. The humic-like FDOM component (Comp.1) was produced by bacteria proportionally to DIN supply. The protein-like FDOM component (Comp.2) was released irrespectively to phytoplankton or bacterial biomass, but depended on DIP and DIN concentrations. Under high DIN supply, Comp.2 was removed by bacterial reworking, leading to an accumulation of humic-like Comp.1. No influence of nutrient availability on amino acid-like FDOM component in peptide form (Comp.3) was observed. Comp.3 potentially acted as an intermediate product during formation or degradation of Comp.2. Our findings suggest that changes in nutrient concentrations may lead to substantial responses in the quantity and quality of optically active DOM and, therefore, might bias results of the applied in situ optical techniques for an estimation of DOC concentrations in open-ocean regions.

Effect of photodegradation on molecular size distribution and quality of dissolved black carbon

The effects of photodegradation on the molecular size distribution and composition of dissolved black carbon (DBC) were explored using a surface water dissolved organic matter (DOM) sample from a terrigenous-influenced, fire-impacted Everglades area canal. The original and photodegraded DOM samples were fractionated using size exclusion chromatography and DBC was quantified via benzene polycarboxylic acid (BPCA) analysis. Size fractionation revealed that DBC was unequally distributed along the DOM molecular weight (MW) continuum and was preferentially associated with high MW (HMW) fractions. The photo-decomposition of HMW DBC generated less condensed DBC photo-products that preferentially re-associated with, and became enriched in, low MW (LMW) DOM size fractions. DBC composition in whole and size-fractionated DOM, as determined from relative BPCA distributions, was not considerably altered with short term photodegradation. This indicated that the size of the conjugated aromatic ring structure may drive the association of DBC compounds with different DOM MW fractions. HMW DBC was also more photo-labile than LMW DBC, which suggests that DBC associated with DOM over a range of size fractions may not exhibit the same degree of photo-reactivity, thereby resulting in different environmental fates for pyrogenic OM.

Effect of DOM Size on Organic Micropollutant Adsorption by GAC.

Granular activated carbon (GAC) adsorption of the micropollutants 2-methylisoborneol (MIB) and warfarin (WFN) at ng/L levels was investigated in five waters with isolated natural dissolved organic matter (DOM) held at a constant dissolved organic carbon concentration. Each water was evaluated for competitive adsorption effects based on the pretreatment of ultrafiltration, coagulation, and additional background micropollutants. Using the breakthrough with unfractionated DOM as a baseline, on average, the water with lower molecular weight (MW) DOM decreased MIB and WFN adsorption capacity by 59%, whereas the water with higher MW DOM increased MIB and WFN adsorption capacity by 64%. All waters showed similar decreasing MIB and WFN adsorption capacity with increasing empty bed contact time (EBCT), with more dramatic effects seen for the more strongly adsorbing WFN. On average, MIB and WFN adsorption kinetics were two times slower in the water with higher MW DOM compared to the water with lower MW DOM, as described by the intraparticle pore diffusion tortuosity. Increased adsorption competition from 27 micropollutants other than MIB and WFN at environmentally relevant concentrations had little to no effect on MIB and WFN breakthrough behavior. Any competitive effect from background micropollutants became indiscernible at longer EBCTs.

High molecular weight dissolved organic matter enrichment selects for methylotrophs in dilution to extinction cultures

The role of bacterioplankton in the cycling of marine dissolved organic matter (DOM) is central to the carbon and energy balance in the ocean, yet there are few model organisms available to investigate the genes, metabolic pathways, and biochemical mechanisms involved in the degradation of this globally important carbon pool. To obtain microbial isolates capable of degrading semi-labile DOM for growth, we conducted dilution to extinction cultivation experiments using seawater enriched with high molecular weight (HMW) DOM. In total, 93 isolates were obtained. Amendments using HMW DOM to increase the dissolved organic carbon concentration 4x (280 μM) or 10x (700 μM) the ocean surface water concentrations yielded positive growth in 4–6% of replicate dilutions, whereas <1% scored positive for growth in non-DOM-amended controls. The majority (71%) of isolates displayed a distinct increase in cell yields when grown in increasing concentrations of HMW DOM. Whole-genome sequencing was used to screen the culture collection for purity and to determine the phylogenetic identity of the isolates. Eleven percent of the isolates belonged to the gammaproteobacteria including Alteromonadales (the SAR92 clade) and Vibrio. Surprisingly, 85% of isolates belonged to the methylotrophic OM43 clade of betaproteobacteria, bacteria thought to metabolically specialize in degrading C1 compounds. Growth of these isolates on methanol confirmed their methylotrophic phenotype. Our results indicate that dilution to extinction cultivation enriched with natural sources of organic substrates has a potential to reveal the previously unsuspected relationships between naturally occurring organic nutrients and the microorganisms that consume them.

Temperature dependence of the photochemical formation of hydroxyl radical from dissolved organic matter.

The temperature dependence of the photochemical production of the hydroxyl radical (•OH) from dissolved organic matter (DOM) was investigated by measuring the apparent temperature dependence of the quantum yield (Φa) for this process. Temperature dependent Φa values were analyzed using the Arrhenius equation. Apparent activation energies obtained for DOM isolates purchased from the International Humic Substances Society ranged from 16 to 34 kJ mol(-1). Addition of 40 units mL(-1) catalase, used to hinder the hydrogen peroxide (H2O2)-dependent pathway to •OH, did not impact the observed activation energy. However, an increase in activation energy was observed in lower molecular weight DOM obtained by size fractionation. We also measured the temperature dependence of p-benzoquionone photolysis as a model compound for DOM and observed no temperature dependence (slope p = 0.41) for the formation of phenol from oxidation of benzene (the •OH probe used), but a value of about 10 kJ mol(-1) for p-benzoquinone loss, which is consistent with formation of a quinone-water exciplex. These data provide insight into DOM photochemistry as well as provide parameters useful for modeling steady state •OH concentrations in natural systems.

Characteristics of dissolved organic matters in submerged membrane bioreactor with low-concentration Cr(VI)

Hexavalent chromium (Cr(VI)) is a common heavy metal, but is hazardous to the environment and human body. Low concentration of Cr(VI) (0.4 mg/L) is ubiquitous in municipal wastewaters of China. However, little is known about its effects on dissolved organic matter (DOM) in submerged membrane bioreactors (MBRs). The effects of low concentration of Cr(VI) on the characteristics of DOM in submerged MBRs were investigated in this study. Compared with control MBR conditions, results showed that low-concentration Cr(VI) caused an increase in concentrations of dissolved organic carbon, polysaccharides, and proteins. Low-concentration Cr(VI) also increased the concentrations of humic substances and protein-like substances, and inhibited the formation of macromolecules (over 500 kDa) in DOM, further enhancing membrane fouling. The low molecular weight (<500 kDa) DOM led to irreversible membrane pore blocking and serious membrane fouling. Additionally, the shifting of DOM functional groups (shift from 3,200 to 3,700 cm−1, shift from 1,640 to 1,626 cm−1, minor change at 1,383.4 and 671–601.4 cm−1) indicated that amino, carboxyl, and sulfonate functionalities were involved in the connection between Cr(VI) and DOM.

Concentrations and Distributions of Metals Associated with Dissolved Organic Matter from the Suwannee River (GA, USA)

Concentrations and distributions of metals in Suwannee River (SR) raw filtered surface water (RFSW) and dissolved organic matter (DOM) processed by reverse osmosis (RO), XAD-8 resin (for humic and fulvic acids [FA]), and XAD-4 resin (for “transphilic” acids) were analyzed by asymmetrical flow field-flow fractionation (AsFlFFF). SR samples were compared with DOM samples from Nelson's Creek (NLC), a wetland-draining stream in northern Michigan; previous International Humic Substances Society (IHSS) FA and RO samples from the SR; and an XAD-8 sample from Lake Fryxell (LF), Antarctica. Despite application of cation exchange during sample processing, all XAD and RO samples contained substantial metal concentrations. AsFlFFF fractograms allowed metal distributions to be characterized as a function of DOM component molecular weight (MW). In SR RFSW, Fe, Al, and Cu were primarily associated with intermediate to higher than average MW DOM components. SR RO, XAD-8, and XAD-4 samples from May 2012 showed similar MW trends for Fe and Al but Cu tended to associate more with lower MW DOM. LF DOM had abundant Cu and Zn, perhaps due to amine groups that should be present due to its primarily algal origins. None of the fractograms showed obvious evidence for mineral nanoparticles, although some very small mineral nanoparticles might have been present at trace concentrations. This research suggests that AsFlFFF is important for understanding how metals are distributed in different DOM samples (including IHSS samples), which may be key to metal reactivity and bioavailability.

Determination of diffusion coefficients of dissolved organic matter in the Churchill River estuary system, Hudson Bay (Canada)

Environmental context Reliable interpretation of metal levels measured by diffusive gradients in thin film (DGT) requires a sound understanding of the diffusion properties of dissolved organic matter (DOM), the main ligand of metals in natural waters. The present study determined that the molecular weight of DOM and conductivity are the main factors controlling the diffusion of freshly collected estuarine DOM across the DGT diffusive gel. Abstract Diffusion coefficients (D) and the molecular weight distribution (MW) of 18 dissolved organic matter (DOM) samples collected in the Churchill River estuary system (Manitoba, Canada) were determined using a diffusive cell apparatus. NaN3 addition has been shown to preserve the DOM MW distribution within 5 weeks of collection whereas the diffusive properties (i.e. D) were strongly influenced by storage conditions, suggesting D must be determined on freshly collected material. Aquatic DOM from the river and estuarine sites was capable of diffusing across a polyacrylamide diffusive gel membrane with mean D values ranging from 2.74×10–6 to 6.98×10–6cm2s–1 and from 2.42×10–6 to 10.7×10–6cm2s–1 respectively, congruent with previous studies using humic substances and natural DOM. The molecular weight of the river and estuary DOM samples (~400–830Da) measured using asymmetrical flow-field flow fractionation (AF4) strongly influenced D, with larger MW DOM having lower D values. Conductivity had a significant negative correlation with D in estuarine samples collected at high and low tides (R2=0.82 and 0.46 respectively). These results suggest that MW and conductivity can significantly influence D of DOM in river and marine-dominated sites respectively.

Qualitative changes of riverine dissolved organic matter at low salinities due to flocculation

AbstractThe flocculation of dissolved organic matter (DOM) was studied along transects through three boreal estuaries. Besides the bulk concentration parameters, a suite of DOM quality parameters were investigated, including colored DOM (CDOM), fluorescent DOM, and the molecular weight of DOM as well as associated dissolved iron concentrations. We observed significant deviations from conservative mixing at low salinities (&lt;2) in the estuarine samples of dissolved organic carbon (DOC), UV absorption (a(CDOM254)), and humic‐like fluorescence. The maximum deviation from conservative mixing for DOC concentration was −16%, at salinities between 1 and 2. An associated laboratory experiment was conducted where an artificial salinity gradient between 0 and 6 was created. The experiment confirmed the findings from the estuarine transects, since part of the DOC and dissolved iron pools were transformed to particulate fraction (&gt;0.2 µm) and thereby removing them from the dissolved phase. We also measured flocculation of CDOM, especially in the UV region of the absorption spectrum. Protein‐like fluorescence of DOM decreased, while humic‐like fluorescence increased because of salt‐induced flocculation. Additionally, there was a decrease in molecular weight of DOM. Consequently, the quantity and quality of the remaining DOM pool was significantly changed after influenced to flocculation. Based on these results, we constructed a mechanistic, two‐component flocculation model. Our findings underline the importance of the coastal filter, where riverine organic matter is flocculated and exported to the sediments.

Origins and bioavailability of dissolved organic matter in groundwater

Dissolved organic matter (DOM) in groundwater influences water quality and fuels microbial metabolism, but its origins, bioavailability and chemical composition are poorly understood. The origins and concentrations of dissolved organic carbon (DOC) and bioavailable DOM were monitored during a long-term (2-year) study of groundwater in a fractured-rock aquifer in the Carolina slate belt. Surface precipitation was significantly correlated with groundwater concentrations of DOC, bioavailable DOM and chromophoric DOM, indicating strong hydrological connections between surface and ground waters. The physicochemical and biological processes shaping the concentrations and compositions of DOM during its passage through the soil column to the saturated zone are conceptualized in the regional chromatography model. The model provides a framework for linking hydrology with the processes affecting the transformation, remineralization and microbial production of DOM during passage through the soil column. Lignin-derived phenols were relatively depleted in groundwater DOM indicating substantial removal in the unsaturated zone, and optical properties of chromophoric DOM indicated lower molecular weight DOM in groundwater relative to surface water. The prevalence of glycine, γ-aminobutyric acid, and d-enantiomers of amino acids indicated the DOM was highly diagenetically altered. Bioassay experiments were used to establish DOC-normalized yields of amino acids as molecular indicators of DOM bioavailability in groundwater. A relatively small fraction (8 ± 4 %) of DOC in groundwater was bioavailable. The relatively high yields of specific d-enantiomers of amino acids indicated a substantial fraction (15–34 %) of groundwater DOC was of bacterial origin.

Effects of molecular weight on the diffusion coefficient of aquatic dissolved organic matter and humic substances

In situ measurements of labile metal species using diffusive gradients in thin films (DGT) passive samplers are based on the diffusion rates of individual species. Although most studies have dealt with chemically isolated humic substances, the diffusion of dissolved organic matter (DOM) across the hydrogel is not well understood. In this study, the diffusion coefficient (D) and molecular weight (MW) of 11 aquatic DOM and 4 humic substances (HS) were determined. Natural, unaltered aquatic DOM was capable of diffusing across the diffusive gel membrane with D values ranging from 2.48×10−6 to 5.31×10−6cm2s−1. Humic substances had diffusion coefficient values ranging from 3.48×10−6 to 6.05×10−6cm2s−1, congruent with previous studies. Molecular weight of aquatic DOM and HS samples (∼500–1750Da) measured using asymmetrical flow field-flow fractionation (AF4) strongly influenced D, with larger molecular weight DOM having lower D values. No noticeable changes in DOM size properties were observed during the diffusion process, suggesting that DOM remains intact following diffusion across the diffusive gel. The influence of molecular weight on DOM mobility will assist in further understanding and development of the DGT technique and the uptake and mobility of contaminants associated with DOM in aquatic environments.

2-Nitrophenol reduction promoted by S. putrefaciens 200 and biogenic ferrous iron: The role of different size-fractions of dissolved organic matter

The reduction of nitroaromatic compounds (listed as a priority pollutant) in natural subsurface environments typically coexists with dissimilatory reduction of iron oxides effected by dissolved organic matter (DOM). Investigating the impact of the DOM that influences those reduction processes is crucial for understanding and predicting the geochemical fate of these environmental species. This study investigated the impact of different molecular weight DOM fractions (DMWDs) on the 2-nitrophenol (2-NP) reduction by S. putrefaciens 200 (SP200) and α-Fe2O3 with lactate (excluding electron donor interference). Kinetic measurements demonstrated that 2-NP reduction rates were affected by the redox reactivity of active species under DMWDs (denoted as L-DOM, M-DOM, and H-DOM). The enhanced reduction rates are consistent with the negative shifts in peak oxidation potential values, the increases in HA-like/FA-like values, aromaticity index values and electron transfer capacity values. L-DOM acted mainly as ligands to complex Fe(II), whereas the significant role of H-DOM in reductive reactions should be acting as an electron shuttle, transferring electrons from SP200 to Fe(III) and 2-NP and from biogenic Fe(II) to 2-NP, further accelerating the 2-NP reductions. Those observations provide valuable insights into the role of DOM in the biogeochemical redox processes and the remediation of contaminated soil in a natural environment.

Evaluation of forest disturbance legacy effects on dissolved organic matter characteristics in streams at the Hubbard Brook Experimental Forest, New Hampshire

Dissolved organic matter (DOM) source and composition are critical drivers of its reactivity, impact microbial food webs and influence ecosystem functions. It is believed that DOM composition and abundance represent an integrated signal derived from the surrounding watershed. Recent studies have shown that land-use may have a long-term effect on DOM composition. Methods for characterizing DOM, such as those that measure the optical properties and size of the molecules, are increasingly recognized as valuable tools for assessing DOM sources, cycling, and reactivity. In this study we measured DOM optical properties and molecular weight determinations to evaluate whether the legacy of forest disturbance alters the amount and composition of stream DOM. Differences in DOM quantity and composition due to vegetation type and to a greater extent, wetland influence, were more pronounced than effects due to disturbance. Our results suggest that excitation-emission matrix fluorescence with parallel factor analysis is a more sensitive metric of disturbance than the other methods evaluated. Analyses showed that streams draining watersheds that have been clearcut had lower dissolved organic carbon (DOC) concentrations and higher microbially-derived and protein-like fluorescence features compared to reference streams. DOM optical properties in a watershed amended with calcium, were not significantly different than reference watersheds, but had higher concentrations of DOC. Collectively these results improve our understanding of how the legacy of forest disturbances and natural landscape characteristics affect the quantity and chemical composition of DOM in headwater streams, having implications for stream water quality and carbon cycling.

Compositions and constituents of freshwater dissolved organic matter isolated by reverse osmosis

Dissolved organic matter (DOM) from riverine and lacustrine water was isolated using a reverse osmosis (RO) system. Solid-state 13C nuclear magnetic resonance (13C NMR) was used to quantitatively evaluate the compositions and constituents of DOM, which are compared with previous investigations on marine DOM. Results indicated that concentration factor (CF) was a key metric controlling yield and sorption of DOM on the RO system. The sorption was likely non-selective, based on the 13C NMR and δ13C analyses. Carbohydrates and lipids accounted for 25.0–41.5% and 30.2–46.3% of the identifiable DOM, followed by proteins (18.2–19.8%) and lignin (7.17–12.8%). The freshwater DOM contained much higher alkyl and aromatic C but lower alkoxyl and carboxyl C than marine DOM. The structural difference was not completely accounted for by using structure of high molecular weight (HMW) DOM, suggesting a size change involved in transformations of DOM during the transport from rivers to oceans.

Heavy metal behavior and dissolved organic matter (DOM) characterization of vermicomposted pig manure amended with rice straw.

Vermicomposting is an eco-friendly method for disposing of livestock and poultry manure. In addition, dissolved organic matter (DOM) can serve as a carrier that enhances the migration and transformation of heavy metals. Here, pig manure amended with rice straw was vermicomposted with Eisenia fetida. The DOM content, molecular weight distribution, and spectroscopic properties of the amended pig manure were measured before and after vermicomposting. The Cu and Zn concentrations in the earthworms increased from 8.24 and 17.63 to 40.75 and 362.78 mg/kg separately after vermicomposting, and the earthworms also increased the heavy metal availability in the vermicompost. Relative to the DOM properties of conventional compost, the DOM molecular weight decreased and varied widely following vermicomposting, and the C/N ratio of the DOM in the vermicompost treatments decreased from 10.37 to 8.60. The Fourier transform far-infrared (FTIR) and fluorescence spectra of the DOM indicated that the amounts of oxygen-containing structures increased while the ratio of humic acid to fulvic acid decreased following vermicomposting. Accordingly, the earthworms augmented the heavy metal mitigation risk in the pig manure. This augment potentially resulted from the decreased humic acid-to-fulvic acid (HA/FA) ratio from DOM structural changes.