Weight Dissolved Organic Matter Research Articles

Molecular characteristics of dissolved organic matter regulate the binding and migration of tungsten in porous media

Tungsten (W) is an emerging contaminant that poses potential risks to both the environment and human health. While dissolved organic matter (DOM) can significantly influence the W's environmental behavior in natural aquifers, the mechanisms by which DOM's molecular structure and functional group diversity impact W binding and migration remain unclear. Using molecular weight-fractionated soil and sediment DOM (<1 kDa, 1–100 kDa, and 100 kDa–0.45 μm), this study systematically investigated the relationship between DOM molecular characteristics and tungstate (WO42−) binding properties using multiple spectroscopic methods, including FTIR, fluorescence spectroscopy and XPS. The migration behavior of WO42− in porous media was also investigated through quartz sand column experiments. Results revealed that approximately 75 % of W was controlled by DOM, with over 50 % binding to low molecular weight DOM (<1 kDa). Tungsten bound to medium-high molecular weight DOM (1–100 kDa, >100 kDa) showed a greater propensity for retention, with the >100 kDa fractions demonstrating stronger selective binding to W, exhibiting distribution coefficients (Kmd) of 6.11 L/g and 10.69 L/g, respectively. Further analysis indicated that W primarily binds with aromatic rings, phenolic hydroxyls, polysaccharides, and carboxyl groups in DOM, potentially affecting DOM structural stability and consequently influencing W migration characteristics. Free W migration in quartz sand was primarily controlled by Langmuir monolayer adsorption, leading to local enrichment (Da = 6.83, Rd = 86.98). When bound to DOM, W's migration ability significantly increased (Rd = 8–10), with adsorption shifting to a Freundlich multilayer model, primarily controlled by convective transport (Npe = 27–62> > 1.96), while adsorption effects weakened (Da ≈ 1). This study, for the first time, systematically reveals the regulatory mechanisms of DOM molecular characteristics on tungsten's environmental behavior. It offers crucial parameter support for constructing tungsten migration models and provides important guidance for tungsten pollution risk assessment and remediation strategies.

Improved solid-state 13C and 15N NMR reveals fundamental compositional divide between refractory dissolved organic carbon and nitrogen in the sea

Marine dissolved organic matter (DOM) is one of the largest reservoirs of organic carbon and nitrogen in the world. Yet, despite its global importance, most DOM remains molecularly uncharacterized. Solid-state nuclear magnetic resonance (NMR) spectroscopy of isolated DOM fractions represents one of the most powerful techniques to understand overall structural composition. However, it is well known that standard cross polarization magic angle spinning (CP/MAS) NMR, the technique used for almost all past solid-state NMR studies of DOM, is at best “semi-quantitative,” and underestimates fully substituted NMR active nuclei. Additionally, almost all past solid-state NMR work analyzed high molecular weight (HMW) material isolated by ultrafiltration, which is now understood to represent mostly 14C-young, “semi-labile” compounds. In contrast, there is far less information regarding the composition of older, low molecular weight (LMW) DOM, which represents the vast majority of the ocean’s accumulated refractory DOM pool.Here, we applied 13C and 15N solid-state multiCP/MAS NMR, improved NMR methods optimized to more quantitatively resolve fully substituted NMR nuclei, to both HMW and LMW DOM isolated from the surface and deep North Pacific Subtropical Gyre. These methods confirm past work indicating most nitrogen containing HMW DOM as amide compounds, but also demonstrate a modest heterocyclic N component not previously identified. In contrast, we found that LMW DON is almost entirely aromatic heterocyclic N, consistent with the hypothesis that heterocyclic N structures may be largely responsible for the accumulation of the ocean’s refractory DON pool. Surprisingly, however, we find DOC aromatic functionalities still represent only a very minor portion of either the HMW or the LMW refractory carbon pools, in marked contrast to refractory DON composition. Together, these more quantitative solid-state NMR techniques likely represent the most accurate picture of DON and DOC functional and compound-class makeup to date, and so have broad implications for our understanding of marine DOM structure and cycling. Specifically, our new data suggests that while chemical composition likely acts as a key control on DOM lability, the most refractory components of DOC and DON have very different compositions, sources, and cycling, supporting the idea that DOC and DON cycling in the ocean may be largely decoupled.

Qualitative variability of dissolved organic matter in the Baltic Sea sediments apparent from fluxes and optical properties

IntroductionThe release of dissolved organic matter (DOM) from sediments serves as an important part of the carbon cycle.MethodsHere, we address pore water DOM quality and its release from shallow sediments (0–10 cm) of the central and southern Baltic Sea - Gdansk, Bornholm, and Eastern Gotland Basins - using excitation–emission matrix spectroscopy and size-exclusion chromatography.ResultsDOM release from sediments displayed spatial variability, with diffusive DOC fluxes ranging from 0.02 to 1.06 mmol m−2 d−1, and basin-averaged fluxes increased in the order Gotland &amp;lt; Bornholm &amp;lt; Gdansk. DOM qualitative characteristics also varied among investigated basins. In the oxygen-limited study sites from the Gdansk Basin, we observed elevated abundances of low apparent molecular weight DOM fraction and proteinaceous-like fluorescent DOM, while in the Bornholm Basin, pore water DOM was generally more humic-like and of higher apparent molecular weight. Pore waters from the deepest study sites in the Gotland Basin were qualitatively very similar to those of the pore waters from the upper sediment layers (0–4 cm) from all other investigated sites, suggesting little organic matter reworking at depth at those stations.DiscussionOur results suggest that the spatial variability in the magnitude of DOM release may be linked to the qualitative differences of DOM in sediments.

Characteristics of Soil Organic Carbon and Its Influencing Factors of Different Plant Communities in the Yellow River Delta

Changes in soil organic carbon （SOC） are of great importance to the evolution of soil quality. The distribution characteristics of soil organic carbon （SOC）, easily oxidizable organic carbon （EOC）, dissolved organic carbon （DOC）, and particulate organic carbon （POC） were investigated in the 0-50 cm soil layer of the Phragmites australis, Suaeda salsa, and Tamarix chinensis communities of the supratidal zone in the Yellow River Delta as the research subjects. Then, the composition and sources of soil dissolved organic matter （DOM） were analyzed based on the UV-vis spectroscopy, three-dimensional excitation emission matrix spectroscopy, and parallel factor analysis （PARAFAC）. Finally, the key factors affecting the characteristics of soil organic carbon and DOM fractions of different plant communities were finally revealed in combination with the physicochemical properties of the soil. The results showed that： ① Comparing different communities, the S. salsa community had the highest ω（SOC） at 7.53 g·kg-1, the T. chinensis community had the highest ω（DOC） at 0.98 g·kg-1, and the P. australis community had significantly higher ω（EOC） and ω（POC） than those of the S. salsa and T. chinensis communities at 1.47 g·kg-1 and 0.65 g·kg-1, respectively. The vertical distribution showed a tendency to decrease with deeper soil layers, except for POC concentration. ② The main components of soil DOM of the P. australis, S. salsa, and T. chinensis communities were humus, protein-like substances, and fulvic acid-like substances, of which exogenous components accounted for 55.80%, 56.41%, and 52.81% in the above communities, respectively. ③ Comparing different communities, the humification degree of the P. australis community was significantly higher than that of the S. salsa and T. chinensi communities, but its aromaticity and proportion of biological sources were significantly lower than those of the T. chinensi community. On the vertical profile of the soil, DOM aromaticity and humification degree gradually increased with the deepening of the soil layer, and the deeper soils were mainly dominated by small molecular weight DOM with a lower proportion of hydrophobic fraction. ④ Redundant analysis showed that N （P<0.01）, NO2--N （P<0.01）, and NH4+-N （P<0.05） were the key factors affecting the changes in soil organic carbon and DOM fractions.

Deciphering the spatial heterogeneity of groundwater arsenic in Quaternary aquifers of the Central Yangtze River Basin

Significant spatial variability of groundwater arsenic (As) concentrations in South/Southeast Asia is closely associated with sedimentogenesis and biogeochemical cycling processes. However, the role of fine-scale differences in biogeochemical processes under similar sedimentological environments in controlling the spatial heterogeneity of groundwater As concentrations is poorly understood. Within the central Yangtze Basin, dissolved organic matter (DOM) and microbial functional communities in the groundwater and solid-phase As-Fe speciation in Jianghan Plain (JHP) and Jiangbei Plain (JBP) were compared to reveal mechanisms related to the spatial heterogeneity of groundwater As concentration. The optical signatures of DOM showed that low molecular terrestrial fulvic-like with highly humified was predominant in the groundwater of JHP, while terrestrial humic-like and microbial humic-like with high molecular weight were predominant in the groundwater of JBP. The inorganic carbon isotope, microbial functional communities, and solid-phase As-Fe speciation suggest that the primary process controlling As accumulation in JHP groundwater system is the degradation of highly humified OM by methanogens, which drive the reductive dissolution of amorphous iron oxides. While in JBP groundwater systems, anaerobic methane-oxidizing microorganisms (AOM) coupled with fermentative bacteria, iron reduction bacteria (IRB), and sulfate reduction bacteria (SRB) utilize low molecular weight DOM degradation to drive biotic/abiotic reduction of Fe oxides, further facilitating the formation of carbonate associated Fe and crystalline Fe oxides, resulting in As release into groundwater. Different biogeochemical cycling processes determine the evolution of As-enriched aquifer systems, and the coupling of multiple processes involving organic matter transformation‑iron cycling‑sulfur cycling-methane cycling leads to heterogeneity in the spatial distribution of As concentrations in groundwater. These findings provide new perspectives to decipher the spatial variability of As concentrations in groundwater.

Impact of organic matter molecular weight on hexavalent chromium enrichment in green microalgae

In lightly polluted water containing heavy metals, organic matter, and green microalgae, the molecular weight of organic matter may influence both the growth of green microalgae and the concentration of heavy metals. This study elucidates the effects and mechanisms by which different molecular weight fractions of fulvic acid (FA), a model dissolved organic matter component, facilitate the bioaccumulation of hexavalent chromium (Cr(VI)) in a typical green alga, Chlorella vulgaris. Findings show that the addition of FA fractions with molecular weights greater than 10 kDa significantly enhances the enrichment of total chromium and Cr(VI) in algal cells, reaching 21.58%−31.09 % and 16.17 %−22.63 %, respectively. Conversely, the efficiency of chromium enrichment in algal cells was found to decrease with decreasing molecular weight of FA. FA molecular weight within the range of 0.22 µm-30 kDa facilitated chromium enrichment primarily through the algal organic matter (AOM) pathway, with minor contributions from the algal cell proliferation and extracellular polymeric substances (EPS) pathways. However, with decreasing FA molecular weight, the AOM and EPS pathways become less prominent, whereas the algal cell proliferation pathway becomes dominant. These findings provide new insights into the mechanism of chromium enrichment in green algae enhanced by medium molecular weight FA.

High-molecular-weight dissolved organic matter enhanced phosphorus availability in paddy soils: Evidence from field and microcosm experiments

Dissolved organic matter (DOM) derived from organic fertilizers may increase soil phosphorus (P) availability. However, the frequently observed correlation between soil P availability and dissolved organic carbon (DOC) content has led to an excessive focus on DOC content at the expense of DOM properties. The present study investigated the influence of DOM characteristics on soil P availability by using a 6-year field experiment and microcosms of P sorption in paddy soil. Our results showed that partial replacement of chemical P fertilizer with manure or crop straw increased P fertilizer-use efficiency, even when decreasing chemical P input by 34%, compared to normal chemical fertilization. The microcosm experiment demonstrated that DOM properties, rather than total DOC content, determine soil P sorption capacity, despite the significant correlation between DOC content and P availability observed in the field experiment. Manure-DOM exerted stronger inhibitory effects on P sorption than straw-DOM, and high molecular weight (HMW)-fractionated DOM exerted stronger inhibitory effects on P sorption than low-molecular-weight-fractionated DOM by 16–20%. The mechanism is primarily attributed to high molecular weight (HMW) DOM, which possesses unique characteristics such as strong aromaticity. These attributes lead to competition for soil P sorption sites and a decrease in soil surface charge, collectively suppressing P sorption in paddy soil. Our study points out a promising avenue for regulating organic matter properties with organic fertilization to improve P use efficiency in agricultural soils.

Dissolved organic matter influences the indigenous bacterial community and polycyclic aromatic hydrocarbons biodegradation in soils

In polycyclic aromatic hydrocarbon (PAH) contaminated soils, bioremediation is superior to other strategies owing to its low cost and environmental friendliness. However, dissolved organic matter (DOM) and indigenous bacterial communities can affect the efficiency of PAH-degrading bacteria (PDB). This study found that exogenous PDB (C1) including the genera Acinetobacter, Stenotrophomonas, and Comamonas, decreased the bacterial diversity of Alfisol, Ultisol, Inceptisol, and Mollisol, and DOM enhanced the diffusion of PDB and the bioavailability of PAH. In addition, bacteria preferred to ingest low molecular weight DOM fractions, and the abundances of lipid-like and protein-like substances decreased by 0.12–3.03 % and 1.73–4.60 %. The DOM fractions had a more marked influence on the indigenous bacteria than the exogenous PDB, and PDB dominated the PAH biodegradation process in the soils. More COO functional groups promoted the utilization of higher molecular weight-related homologue fractions by bacteria, and lower molecular weight fractions carrying more CH2 functional groups declined during biodegradation. This study investigated the variations in bacterial communities during biodegradation and revealed the effects of DOM fractions on biodegradation in PAH-contaminated soils at the molecular level. These results will promote the development of bioremediation strategies for organics-contaminated soil and provide guidance for prediction models of soil biodegradation kinetics.

Biodegradability of unheated and laboratory heated dissolved organic matter.

Following wildfires, partially combusted biomass remains on the forest floor and erosion from the landscape can release dissolved pyrogenic organic matter (dPyOM) to surface waters. Therefore, post-fire alterations to dissolved organic matter (DOM) in aquatic systems may play a vital role in DOM stability and biogeochemical cycles. Dissolved PyOM biodegradation remains poorly understood and is expected to vary with combustion temperature and fuel source. In this study laboratory heating and leaching of forest floor materials (soil and litter) were used to compare the biodegradability of unheated, low (250 °C), and moderate (450 °C) temperature leachates. Inoculation experiments were performed with river microbes. Dissolved organic carbon (DOC) and nitrogen (DON), inorganic nitrogen, and DOM optical properties were monitored for 38 days. Inoculation experiments showed significantly greater DOC biodegradation of low and moderate temperature samples (64% and 71%, respectively) compared to unheated samples (32%). The greater DOC biodegradation may be explained by lower molecular weight DOM composition of heated leachates which was supported by higher initial E2/E3 ratios (absorbance at 250 nm/365 nm). Further, the observed decrease in the E2/E3 ratio after incubation suggests biodegradation of smaller compounds. This trend was greater for heated samples than unheated DOM. Specific ultraviolet absorbance increased after incubation, suggesting biodegradation of aliphatic compounds. Inoculated moderate temperature samples showed the greatest DON degradation (74%), followed by low temperature (58%) and unheated (51%) samples. Overall, results suggest that low and moderate temperature dPyOM was more biodegradable than unheated DOM, which may have implications for aquatic biogeochemical cycling, ecosystem function, and water quality in fire-impacted watersheds.

Effect of the molecular weight of DOM on the indirect photodegradation of fluoroquinolone antibiotics

Dissolved organic matter (DOM) is ubiquitous and widespread in natural water and influences the transformation and removal of antibiotics. Nevertheless, the influence of DOM molecular weight (MW) on the indirect photodegradation of antibiotics has rarely been reported. This study attempted to explore the influence of the molecular weight of DOM on the indirect photodegradation of two fluoroquinolone antibiotics (FQs), ofloxacin (OFL) and norfloxacin (NOR), by using UV–vis absorption and fluorescence spectroscopy. The results showed that indirect photodegradation was considered the main photodegradation pathway of FQs in DOM fractions. Triplet-state excited organic matter (3DOM*) and singlet oxygen (1O2) were the main reactive intermediates (RIs) that affected the indirect photodegradation of FQs. The indirect photodegradation rate of FQs was significantly promoted in DOM fractions, especially in the low molecular weight DOM fractions (L-MW DOM, MW < 10 kDa). The results of excitation-emission matrix spectroscopy combined with parallel factor analysis (EEM-PARAFAC) showed that terrestrial humic-like substances had a higher humification degree and fluorophore content in L- MW DOM fractions, which could produce more 3DOM* and 1O2 to promote the indirect photodegradation of FQs. This study provided new insight into the effects of DOM at the molecular weight level on the indirect photodegradation of antibiotics in natural water.

Controls on the composition of dissolved organic matter in treatment wetland source waters of South Florida, USA

Dissolved organic matter (DOM) plays an important role in the phosphorus (P) and nitrogen (N) cycle, but the examination of coupled biogeochemical cycling in treatment wetlands, like the Everglades Stormwater Treatment Areas (STAs), has been limited. Here, we studied eight STA inflow waters to gain insights into the production and potential photo- and biolability of DOM in surface waters flowing into these treatment wetlands. A suite of optical and fluorometric indices was coupled with amino acid and bulk elemental analyses to evaluate differences in inflow water quality for particulate organic matter (POM), DOM (<0.2 μm), and high and low molecular weight DOM (HMW-DOM and LMW-DOM). A photochemical experiment was conducted with these inflow waters to assess how solar exposure alters DOM turnover and its relationship with nutrient concentrations, and to evaluate the influence of photochemistry on potential STA performance. The DOM of STA inflow water was predominantly composed of allochthonous terrestrial sources, and the LMW-DOM fraction represented 70 to 94% of the total DOM pool. Inflow waters separated along the biophysical dimension of our PCA based on their photolability and bioavailability, driven by differences in the inflow water's DOM composition. UV exposure decreased humic and aromaticity proxies with concomitant photo-production of LMW compounds and increases in bioavailability proxies. Photo-exposure significantly decreased nitrate and dissolved organic carbon (DOC) concentrations for most of the sites and dissolved organic N (DON) for three of the eight sites, but no significant changes were noted for ammonia. One site exhibited an increase in nitrate with UV exposure and had DOM primarily from terrestrial origins. Spectroscopic indices, PARAFAC components, and amino acids provided corroborating evidence that further supported the differences in photo- and biolability at each inflow site, which is likely driven by their original DOM characteristics. PARAFAC components were correlated with dissolved organic P (DOP) and suggest that there may be adsorption of DOP with humic components in the LMW fraction. This work highlights the importance of photochemistry in the STAs, the complexity of DOM turnover in STA source waters, and the potential interactions between dissolved P and other DOM components, which may further influence the treatment efficiency of the STAs.

Solid phase extraction of ocean dissolved organic matter with PPL cartridges: efficiency and selectivity

Our current knowledge of the chemical composition of ocean dissolved organic matter (DOM) is limited, mainly because of its extreme molecular diversity, low concentration of individual compounds and the elevated ionic strength of ocean waters. As a result, many analytical methods require a previous extraction step. The efficiency and selectivity of the extraction method defines the representativeness of the extracted DOM fraction. Nowadays, the most widespread procedure for concentrating DOM is solid phase extraction (SPE) using styrene divinyl benzene polymer cartridges (PPL). Here, we investigate the effect of SPE-PPL on DOM elemental and optical properties to assess the efficiency and selectivity of this extraction method on water samples from the main intermediate and deep water masses of Arctic, Mediterranean and Antarctic origin present in the Cape Vert Frontal Zone (CVFZ, NW Africa). Furthermore, North and South Atlantic Central waters converge in this area and coastal DOM is injected by the giant upwelling filament of Cape Blanc. On one side, the colored fraction of DOM (CDOM) presented extraction efficiencies comparable to that of the bulk dissolved organic carbon (DOC), but decreased significantly with increasing wavelength, suggesting an affinity of PPL cartridges for low molecular weight organic compounds. While the protein-like fluorescent fraction of DOM (FDOM) was also extracted with the same efficiency than DOC, the extraction efficiency of the humic-like fraction was comparatively much higher. On the other side, dissolved organic nitrogen (DON) extraction efficiencies were about half that of DOC. These contrasting extraction efficiencies of the different DOM pools indicated that the extracts were enriched in N-poor, low molecular weight and recalcitrant DOM, therefore showing less variability than the corresponding bulk DOM. Furthermore, DOC, DON, CDOM and FDOM extracted were not homogeneous through the water column but displayed certain significant differences among water masses in both efficiency and selectivity.

DOM influences Hg methylation in paddy soils across a Hg contamination gradient

Rice paddies provide optimum conditions for Hg methylation, and paddy soil is a hot spot for Hg methylation and the predominant source of methylmercury (MeHg) accumulated in rice grains. The role of dissolved organic matter (DOM) in controlling Hg bioavailability and methylation in rice paddy systems remains unclear. Paddy soils from eight various cultivation sites in China were chosen to investigate the variations in soil DOM and the influence of DOM concentration and optical characteristics on Hg methylation in rice paddy systems. In the present study, 151 rhizosphere soil samples were collected, and UV–Vis absorption and fluorescent spectroscopy were used to identify the optical properties of DOM. The relationship between MeHg and DOM's optical property indices revealed the production of MeHg consumes lower molecular weight DOM. Moreover, the correlation between DOM concentration and its optical characteristics highlighted the significant role of humic components on MeHg variability in paddy soil. Variation and correlation results demonstrated the allochthonous origin of DOM in the Hg-contaminated soil, with a higher molecular weight and humic character of DOM, as well as the dominant role of autochthonous DOM in promoting Hg methylation in uncontaminated soil. The current study indicated that soil organic matter and its dissolved fractions tend to limit Hg bioavailability and subsequently diminish MeHg production in contaminated paddy soils. Furthermore, the leading roles of allochthonous DOM in protecting MeHg from degradation and autochthonous DOM signatures in enhancing MeHg production in paddy soils. Overall, these findings provide insight into the correlative distributions of DOM and Hg along a Hg concentration gradient in paddy soil, thereby highlighting their potential role in controlling Hg bioavailability and regulating Hg methylation in the soil ecosystems.

Role of lake dissolved organic matter in cyanobacteria removal by cationic polyacrylamide flocculation and screen filtration

Prompt removal of densely accumulated cyanobacteria is a straightforward method to alleviate the harm of cyanobacterial blooms to lakes. In this study, a cyanobacteria harvesting ship based on flocculation and filtration was used for the removal of cyanobacteria in a bay of Dianchi Lake (Yunnan Province, China), in which the fate and influence of lake dissolved organic matter (DOM) were investigated. After flocculation with 1–3 mg/L cationic polyacrylamide (CPAM) and filtration with the 100-µm-pore-sized screens of a rotary drum filter (RDF), >90 % of cyanobacteria was removed and the DOM was slightly reduced from 7.83 mg/L to 4.61 ∼ 6.49 mg/L. Tryptophan protein-like and high molecular weight (MW) DOM was selectively removed, increasing the humification index and decreasing the biological index in the treated water. Lake DOM, especially the high MW fractions of lake DOM, played an important role in CPAM flocculation. Cyanobacteria could not be effectively flocculated in Milli-Q water while the removal efficiency increased to over 90 % when 1–3 mg/L high MW DOM of Dianchi Lake was added. Three lakes in Yunnan Province were also plagued by cyanobacterial blooms, including Erhai Lake, Qilu Lake, and Xingyun Lake. The high MW DOM (1.7–2.7 mg/L) in the lakes could also deduce the effective flocculation of cyanobacteria with CPAM. The flocculation mechanism could function by the interactions of quaternary ammonium groups of CPAM and carboxylate groups of high MW DOM that form net-like polyelectrolyte complexes (PECs), and coexisting cyanobacteria cells were encapsulated into the PECs, leading to the formation of large flocs under stirring conditions. In the lakes with high densities of cyanobacteria, there might be enough high-MW DOM to promote the flocculation of CPAM, and after flocculation-filtration treatment, both cyanobacteria and cyanobacteria-deprived DOM were effectively removed.

Dissolved organic metabolite extraction from high-salt media.

We describe considerations and strategies for developing a nuclear magnetic resonance (NMR) sample preparation method to extract low molecular weight metabolites from high-salt spent media in a model coculture system of phytoplankton and marine bacteria. Phytoplankton perform half the carbon fixation and oxygen generation on Earth. A substantial fraction of fixed carbon becomes part of a metabolite pool of small molecules known as dissolved organic matter (DOM), which are taken up by marine bacteria proximate to phytoplankton. There is an urgent need to elucidate these metabolic exchanges due to widespread anthropogenic transformations on the chemical, phenotypic, and species composition of seawater. These changes are increasing water temperature and the amount of CO2 absorbed by the ocean at energetic costs to marine microorganisms. Little is known about the metabolite-mediated, structured interactions occurring between phytoplankton and associated marine bacteria, in part because of challenges in studying high-salt solutions on various analytical platforms. NMR analysis is problematic due to the high-salt content of both natural seawater and culture media for marine microbes. High-salt concentration degrades the performance of the radio frequency coil, reduces the efficiency of some pulse sequences, limits signal-to-noise, and prolongs experimental time. The method described herein can reproducibly extract low molecular weight DOM from small-volume, high-salt cultures. It is a promising tool for elucidating metabolic flux between marine microorganisms and facilitates genetic screens of mutant microorganisms.

The desorption mechanism of dissolved organic matter on pollutants and the change of biodiversity during sediment dredging

Sediment dredging is an effective means to control the endogenous pollution of lakes, which could significantly change the concentration and composition of organic matter, especially dissolved organic matter (DOM) in the lake. DOM is particularly important for the release of endogenous pollutants, which will inevitably bring an impact on aquatic biodiversity. Nevertheless, in recent research little attention has been paid to the desorption mechanism of DOM on pollutants and the change of biodiversity during dredging. This study investigated the physicochemical properties of DOM in the sediment by taking a sediment dredging project in Dianchi Lake in China for example. The correlations of DOM properties with the desorption behavior of nitrogen (N), phosphorus (P), cadmium (Cd), lead (Pb) and the biodiversity of aquatic organisms were analyzed. The results show that the aromaticity and humification of DOM were improved after dredging, and the high molecular weight DOM was degraded into low molecular weight substance. The desorption amount of N, P and heavy metals (Cd, Pb) were decreased as the pH values increased. Moreover, NH4+-N promoted the release of Pb2+ from DOM, while the release of PO43--P was inhibited. Correlation analysis shows that the physicochemical properties of DOM exactly affected the release of N, P, Cd and Pb. It was easier to desorb pollutants with low aromaticity and humification of DOM, leading to a decrease in the diversity of aquatic organisms. This study identified the desorption mechanism of endogenous pollutants in DOM and the ecological risk to aquatic organisms, providing a theoretical basis for the prevention and control of water pollution.

Tracing carbon and nitrogen microbial assimilation in suspended particles in freshwaters

The dynamic interactions between dissolved organic matter (DOM) and particulate organic matter (POM) are central in nutrient cycling in freshwater ecosystems. However, the molecular-level mechanisms of such interactions are still poorly defined. Here, we study spatial differences in the chemical (i.e., individual proteinaceous amino acids) and microbial (i.e., 16S rRNA) composition of suspended sediments in the River Chew, UK. We then applied a compound-specific stable isotope probing (SIP) approach to test the potential assimilation of 13C,15N-glutamate (Glu) and 15N-NO3− into proteinaceous biomass by particle-associated microbial communities over a 72-h period. Our results demonstrate that the composition of suspended particles is strongly influenced by the effluent of sewage treatment works. Fluxes and percentages of assimilation of both isotopically labelled substrates into individual proteinaceous amino acids showed contrasting dynamics in processing at each site linked to primary biosynthetic metabolic pathways. Preferential assimilation of the organic molecule glutamate and evidence of its direct assimilation into newly synthesised biomass was obtained. Our approach provides quantitative molecular information on the mechanisms by which low molecular weight DOM is mineralised in the water column compared to an inorganic substrate. This is paramount for better understanding the processing and fate of organic matter in aquatic ecosystems.

Chemodiversity of dissolved organic matter in cadmium-contaminated paddy soil amended with different materials

Dissolved organic matter (DOM) in soil is a key factor affecting the bioavailability of heavy metals, but very few studies have focused on the role of DOM in the use of soil amendments to mitigate heavy metal accumulation in crops. Here, eleven materials were added to cadmium (Cd)-contaminated paddy soil in greenhouse pot trials; rice was grown and harvested, the chemodiversity of post-harvest soil DOM was characterized using Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry, and the specific associations between soil DOM traits and water-extractable soil Cd concentration were identified at the molecular level. The results showed that the endogenous release caused by altering soil pH had a greater effect on soil DOM concentration than did the exogenous chemical input due to the application of organic amendments, which in turn contributed to the chemodiversity of DOM. After one season of rice cultivation, soil DOM molecules were mainly dominated by relatively low molecular weight heteroatom-free lignins. C/N, C/H ratios of organic materials influenced DOM molecular fingerprint patterns, and soil pH and redox potential were the main driving forces affecting the chemodiversity of DOM. Furthermore, the low molecular weight, high saturation, low aromaticity, and heteroatom-free DOM molecules are more likely to dissolve Cd from the soil solid phase, thus increasing the potential risk of Cd to the environment. The results provide critical information about amendments-induced changes in DOM chemodiversity and will inform the selection of appropriate soil amendments.

Leveraging DOM UV absorbance and fluorescence to accurately predict and monitor short-chain PFAS removal by fixed-bed carbon adsorbers

Carbon adsorbent fouling by dissolved organic matter (DOM) inhibits the ability of the widely-used rapid small-scale column test (RSSCT) to accurately predict the removal of organic micropollutants (OMP) from water by full-scale carbon adsorbers. Here, the adsorption of 11 short-chain per-/poly-fluoroalkyl substances (PFAS) from groundwater, surface water, and wastewater was examined in pilot columns as well as RSSCTs using constant diffusivity (CD) and proportional diffusivity (PD) designs. Neither the CD- or PD-RSSCT accurately predicted pilot adsorber breakthrough of PFAS using standard diffusional mass transfer models. However, PFAS breakthrough relative to optical property (e.g., peak C, UV absorbance at 254 nm) breakthrough remained constant between pilot column, CD-RSSCT, and PD-RSSCT designs. This finding permitted accurate breakthrough predictions for the sum of PFAS and for 9 of the 11 PFAS on an individual basis in pilot columns using RSSCTs. Multiple linear regressions incorporating influent and treated water optical parameters enabled the modeling approach to be applied to water sources with heterogeneous DOM characteristics. It is hypothesized that this methodology was successful because (i) optical parameters adequately quantified the competitive nature of DOM and their adsorption behaved similar to OMP and (ii) competitive adsorption by low-molecular weight DOM was the predominant fouling mechanism. An OMP monitoring approach was developed for waters containing DOM with heterogenous characteristics that also relied on raw and treated water optical properties. UVA254 and fluorescence monitoring could therefore enable water treatment to remove PFAS in a variety of scenarios that face inhibitory cost and analytical limitations, such as decentralized and low-resource settings.

Interaction between polychlorinated biphenyls and dissolved organic matter of different molecular weights from natural and anthropic sources

Polychlorinated biphenyls (PCBs) are compounds of significant interest due to high toxicity, persistence, long-range atmospheric transport, and bioaccumulation. These compounds can interact with components present in the environment, including dissolved organic matter (DOM) in soils and waters, thereby modifying its availability and movement. In this study, DOM was fractionated by ultrafiltration and characterized according to its hydrophobicity and hydrophilicity, then the interaction of a series of PCBs and different DOM fractions was evaluated. The DOM was collected from the surface waters of three sectors located along a river in the southern part of America. These sectors are subject to different anthropic activities, thus the DOM of sector 1, with the least anthropic influence, was mainly hydrophobic and with a high content of aromatic structures. In contrast, the DOM collected from sectors 2 and 3, where anthropic activity is highest, was slightly hydrophobic and hydrophilic, respectively. The DOM of these two sectors was mainly composed of low molecular weight macromolecules. These results revealed that more hydrophobic PCBs (i.e., 101, 118, 138, and 180) have a greater affinity to DOM with a higher molecular weight (i.e., >1 kDa). In turn, PCBs with lesser chlorination and hydrophobicity presented a greater affinity to DOM with a lower molecular weight. In conclusion, our study shows that the high molecular weight DOM is responsible for mobilizing PCBs with a high degree of chlorination.