Dissolved organic matter (DOM) is ubiquitous and plays an important role in regulating water quality, ecological function, and the fate and transport of trace elements and pollutants in aquatic ...environments. Both the colloidal precursors (i.e. <1 kDa) and bulk DOM collected from a freshwater estuary were incubated in the dark for 21 days to examine dynamic changes in molecular size and composition induced by microbial degradation and self-assembly. Results showed that the concentrations of total organic carbon, carbohydrates, and protein-like substances decreased by 11–30% during incubation, while those of humic- and fulvic-like substances remained relatively constant, indicating humic substances are more resistant to microbial utilization compared to carbohydrates and protein-like DOM. Despite the different extents in decline, these DOM components had a similar transformation pathway from the <1 kDa to colloids (1 kDa–0.45 μm) and further to microparticles (>0.45 μm). Overall, carbohydrates and protein-like substances, especially the high molecular weight components, were preferentially decomposed by microorganisms whereas humic- and fulvic-like DOM components significantly coagulated through abiotic self-assembly. The contrasting degradation/transformation pathways between the humic-like and protein-like substances along the size continuum, as also characterized by flow field-flow fractionation analysis, demonstrated that the dynamic transformation and degradation of DOM is regulated by both molecular size and organic composition. This finding provides new insights into the biogeochemical cycling pathways of heterogeneous DOM and its environmental fate and ecological role in aquatic systems.
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•Aquatic DOM transformation between different size fractions and components was quantified in the lab.•DOM can be actively transferred from LMW to colloids and microparticles during incubation.•DOM transformation was related to both molecular-size and chemical composition.•Self-assembly is mainly responsible for changes in size distribution of humic-like DOM.•Microbial processes preferentially degraded protein-like and CHO components.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Phosphorus (P) concentrations and primary production in the Great Lakes have declined since the 1980s, but changes in biogeochemical cycling pathways of different P species remain poorly understood. ...Water samples were collected for the measurements of different P species to examine the dynamics of P in the water column across the river-lake interface from the Milwaukee River to open Lake Michigan. Dissolved inorganic P (DIP) concentrations were as high as 3049 nM in river waters, but decreased dramatically to as low as 11 ± 7 nM in open lake waters. Total dissolved P was mostly measured in the form of DIP in river waters (73% ± 18%), whereas dissolved organic P (DOP) became the predominant species (85% ± 18%) in lake waters. Colloidal P (>1 kDa) comprised 58% ± 16% of the bulk DOP in river waters, but decreased to 23% ± 5% in ologotrophic lake waters, showing again contrasting biogeochemical regimes between river and lake waters. Biological processes and coagulation/sedimentation were largely responsible for the removal of river-derived P species and active transformation between inorganic and organic P occurred in both dissolved and particulate phases across the river-lake interface. Increased water column P inventory over the winter of 2013–2014 likely resulted from an accumulative effect of both atmospheric and riverine inputs in the upper water column, and benthic nepheloid layer processes coupled with quagga mussels excretion for the lower water column, respectively. High partition coefficient values (logK
d of 4.33–7.01) and a “particle concentration effect” on the partitioning of P between dissolved and particulate phases attested the particle-reactive nature of P in lake waters.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NMLJ, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK
•The performance of a FlFFF system was systematically evaluated.•Three different membranes’ cutoffs were calibrated using macromolecular standards.•The effect of membrane's cutoffs and carrier ...solutions on DOM separation was examined.•Natural DOM is heterogeneous in size and chemical composition.
Colloidal retention characteristics, recovery and size distribution of model macromolecules and natural dissolved organic matter (DOM) were systematically examined using an asymmetrical flow field-flow fractionation (AFlFFF) system under various membrane size cutoffs and carrier solutions. Polystyrene sulfonate (PSS) standards with known molecular weights (MW) were used to determine their permeation and recovery rates by membranes with different nominal MW cutoffs (NMWCO) within the AFlFFF system. Based on a ≥90% recovery rate for PSS standards by the AFlFFF system, the actual NMWCOs were determined to be 1.9kDa for the 0.3kDa membrane, 2.7kDa for the 1kDa membrane, and 33kDa for the 10kDa membrane, respectively. After membrane calibration, natural DOM samples were analyzed with the AFlFFF system to determine their colloidal size distribution and the influence from membrane NMWCOs and carrier solutions. Size partitioning of DOM samples showed a predominant colloidal size fraction in the <5nm or <10kDa size range, consistent with the size characteristics of humic substances as the main terrestrial DOM component. Recovery of DOM by the AFlFFF system, as determined by UV-absorbance at 254nm, decreased significantly with increasing membrane NMWCO, from 45% by the 0.3kDa membrane to 2–3% by the 10kDa membrane. Since natural DOM is mostly composed of lower MW substances (<10kDa) and the actual membrane cutoffs are normally larger than their manufacturer ratings, a 0.3kDa membrane (with an actual NMWCO of 1.9kDa) is highly recommended for colloidal size characterization of natural DOM. Among the three carrier solutions, borate buffer seemed to provide the highest recovery and optimal separation of DOM. Rigorous calibration with macromolecular standards and optimization of system conditions are a prerequisite for quantifying colloidal size distribution using the flow field-flow fractionation technique. In addition, the coupling of AFlFFF with fluorescence EEMs could provide new insights into DOM heterogeneity in different colloidal size fractions.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
The recent warming in the Arctic is affecting a broad spectrum of physical, ecological, and human/cultural systems that may be irreversible on century time scales and have the potential to cause ...rapid changes in the earth system. The response of the carbon cycle of the Arctic to changes in climate is a major issue of global concern, yet there has not been a comprehensive review of the status of the contemporary carbon cycle of the Arctic and its response to climate change. This review is designed to clarify key uncertainties and vulnerabilities in the response of the carbon cycle of the Arctic to ongoing climatic change. While it is clear that there are substantial stocks of carbon in the Arctic, there are also significant uncertainties associated with the magnitude of organic matter stocks contained in permafrost and the storage of methane hydrates beneath both subterranean and submerged permafrost of the Arctic. In the context of the global carbon cycle, this review demonstrates that the Arctic plays an important role in the global dynamics of both CO₂ and CH₄ . Studies suggest that the Arctic has been a sink for atmospheric CO₂ of between 0 and 0.8 Pg C/yr in recent decades, which is between 0% and 25% of the global net land/ocean flux during the 1990s. The Arctic is a substantial source of CH₄ to the atmosphere (between 32 and 112 Tg CH₄/yr), primarily because of the large area of wetlands throughout the region. Analyses to date indicate that the sensitivity of the carbon cycle of the Arctic during the remainder of the 21st century is highly uncertain. To improve the capability to assess the sensitivity of the carbon cycle of the Arctic to projected climate change, we recommend that (1) integrated regional studies be conducted to link observations of carbon dynamics to the processes that are likely to influence those dynamics, and (2) the understanding gained from these integrated studies be incorporated into both uncoupled and fully coupled carbon-climate modeling efforts.
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BFBNIB, FZAB, GIS, IJS, INZLJ, KILJ, NLZOH, NMLJ, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK, ZRSKP
Green Bay, Lake Michigan, USA, is the largest freshwater estuary in the Laurentian Great Lakes and receives disproportional terrestrial inputs as a result of a high watershed to bay surface area ...ratio. While seasonal hypoxia and the formation of “dead zones” in Green Bay have received increasing attention, there are no systematic studies on the dynamics of dissolved organic matter (DOM) and its linkage to the development of hypoxia. During summer 2014, bulk dissolved organic carbon (DOC) analysis, UV–vis spectroscopy, and fluorescence excitation-emission matrices (EEMs) coupled with PARAFAC analysis were used to quantify the abundance, composition and source of DOM and their spatiotemporal variations in Green Bay, Lake Michigan. Concentrations of DOC ranged from 202 to 571μM-C (average=361±73μM-C) in June and from 279 to 610μM-C (average=349±64μM-C) in August. In both months, absorption coefficient at 254nm (a254) was strongly correlated to bulk DOC and was most abundant in the Fox River, attesting a dominant terrestrial input. Non-chromophoric DOC comprised, on average, ~32% of bulk DOC in June with higher terrestrial DOM and ~47% in August with higher aquagenic DOM, indicating that autochthonous and more degraded DOM is of lower optical activity. PARAFAC modeling on EEM data resulted in four major fluorescent DOM components, including two terrestrial humic-like, one aquagenic humic-like, and one protein-like component. Variations in the abundance of DOM components further supported changes in DOM sources. Mixing behavior of DOM components also indicated that while bulk DOM behaved quasi-conservatively, significant compositional changes occurred during transport from the Fox River to the open bay.
Dynamics of dissolved organic matter in Green Bay, Lake Michigan, USA. Display omitted
•Terrestrial DOM dominated in Green Bay, with increasing aquagenic DOM in late summer.•Non-chromophoric DOC comprised 32% of the bulk DOC in June and 47% in August.•Bulk DOM had a quasi-conservative mixing behavior but underwent compositional changes.•EEM-PARAFAC analysis identified 1 protein-like and 3 humic-like DOM components.•DOM was related to hypoxic condition in southern Green Bay during late summer.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Despite major investments in point source reductions, portions of the Great Lakes, like Green Bay, remain hypereutrophic and are subject to persistent seasonal hypoxia. Phosphorus (P) is generally a ...limiting nutrient in the Great Lakes ecosystem, but not all P species are equally bioavailable, and the dynamics of nutrients and their correlation to algal bloom remain poorly characterized, in part, due to a lack of adequate quantification of P chemical speciation. During summer 2014, water samples were collected from seasonally hypoxic Green Bay for measurements of dissolved and particulate inorganic and organic P to examine P cycling dynamics along a steep nutrient gradient ranging from Fox River inflow dominated eutrophic waters in the southern bay to mesotrophic northern waters near the bay's connection with open Lake Michigan. River-derived dissolved and particulate P was quickly removed from the water column in southern Green Bay through biological uptake and sedimentation. Concentrations of phosphate or dissolved inorganic P (DIP) dramatically decreased from 828±216nM in the Fox River, comprising 57±1% of the total dissolved P, to 24±9nM in northern Green Bay where dissolved organic P (DOP) became predominant (>80%). Generally low phosphate concentrations and extremely high dissolved organic C/P ratios (2090±1160 in August 2014) suggested high DOP turnover rates and active transformation between DOP and DIP through organic degradation during P-limited conditions in Green Bay. Elevated DIP levels were accompanied by low dissolved oxygen in deeper waters (10–15m) of central Green Bay where hypoxia-development occurred, suggesting the release of DIP through particle regeneration under hypoxic conditions enhanced by lateral transport and sediment resuspension. High partition coefficients (Kd) of both inorganic and organic P and their significant negative correlation with suspended particulate matter concentrations indicated the particle-reactive nature of P in freshwater environments and may imply that DOP could also be bioavailable under P-limitation.
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•Dissolved and particulate P speciation was studied in Green Bay, Lake Michigan.•Steep gradients in P species exist from eutrophic river to mesotrophic bay waters.•Low DIP, high DOP and high DOC/DOP ratios were observed throughout Green Bay.•Hypoxia and sediment resuspension appeared to enhance DIP release from sediments.•High particle-reactivity of P may be a factor for P-limitation in lake waters.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Fluorescence excitation emission matrices (EEM) and parallel factor (PARAFAC) analysis have been widely used in the characterization of dissolved organic matter (DOM) in the aquatic continuum. ...However, large sample sets are typically needed for establishing a meaningful EEM-PARAFAC model. Applications of the EEM-PARAFAC technique to individual samples require new approaches. Here, flow field-flow fractionation (FlFFF) combined with offline EEM measurements and PARAFAC analysis was used to elucidate the dynamic changes in DOM composition/optical properties with molecular weight within individual samples. FlFFF-derived size spectra of ultrafiltration-isolated colloidal DOM show that peak-C related fluorophores (E x/E m= 350/450 nm) are present mostly in the 1–3 kDa size range, while peak-T associated fluorophores (E x/E m = 275/340 nm) have a bimodal distribution with peaks in both the 1–3 kDa and the >100 kDa size fractions. The integrated EEM spectra from FlFFF size-fractionated subsamples closely resembled the bulk EEM spectra, attesting to the convincing comparability between bulk and FlFFF size-fractionated EEMs. The PARAFAC-derived DOM components are distinctive among individual samples with the predominant components being humic-like in river water, but protein-like in a highly eutrophic lagoon sample. This compelling new approach combining FlFFF and EEM-PARAFAC can be used to decipher the dynamic changes in size spectra and composition of individual DOM samples from sources to sinks or across the redox/hydrological/trophic interfaces.
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IJS, KILJ, NUK, PNG, UL, UM
Dissolved organic matter (DOM) is ubiquitous in natural waters. The ecological role and environmental fate of DOM are highly related to the chemical composition and size distribution. To evaluate ...size-dependent DOM quantity and quality, water samples were collected from river, lake, and coastal marine environments and size fractionated through a series of micro- and ultra-filtrations with different membranes having different pore-sizes/cutoffs, including 0.7, 0.4, and 0.2 μm and 100, 10, 3, and 1 kDa. Abundance of dissolved organic carbon, total carbohydrates, chromophoric and fluorescent components in the filtrates decreased consistently with decreasing filter/membrane cutoffs, but with a rapid decline when the filter cutoff reached 3 kDa, showing an evident size-dependent DOM abundance and composition. About 70% of carbohydrates and 90% of humic- and protein-like components were measured in the <3 kDa fraction in freshwater samples, but these percentages were higher in the seawater sample. Spectroscopic properties of DOM, such as specific ultraviolet absorbance, spectral slope, and biological and humification indices also varied significantly with membrane cutoffs. In addition, different ultrafiltration membranes with the same manufacture-rated cutoff also gave rise to different DOM retention efficiencies and thus different colloidal abundances and size spectra. Thus, the size-dependent DOM properties were related to both sample types and membranes used. Our results here provide not only baseline data for filter pore-size selection when exploring DOM ecological and environmental roles, but also new insights into better understanding the physical definition of DOM and its size continuum in quantity and quality in aquatic environments.
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•Molecular size-dependent DOM distribution in river, lake and sea waters was studied.•DOM abundance decreased monotonically with decreasing filter/membrane cutoff.•Size-dependent DOM abundance/composition is related to sample and membrane types.•Seawater contained more LMW-DOM compared to river and lake waters.•Different sized DOM characterization can reveal its heterogeneous nature.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Flow field-flow fractionation (FlFFF) coupled on-line with UV absorbance and fluorescence detectors was used to examine the colloidal composition and size distribution of optically active dissolved ...organic matter (DOM) in the lower Mississippi River (MR), the East Pearl River (EPR), the St. Louis Bay (SLB) estuary, and coastal waters of the northern Gulf of Mexico. In addition to field studies, laboratory mixing experiments using river and seawater end-members were carried out to study the processes controlling the estuarine mixing behavior and size partitioning of colloids with different sizes and composition. The colloidal size spectra of chromophoric DOM and humic-like DOM showed one dominant peak in the 0.5-4 nm size range, representing >75% of the total FlFFF-recoverable colloids. In contrast, protein-like DOM showed a bi-modal distribution with peaks at 0.5-4 nm and 4-8 nm, as well as a major portion (from similar to 41% in the EPR to similar to 72% in the Mississippi Bight) partitioned to the >20 nm size fraction. Bulk DOM was lower in abundance and molecular-weight in the MR compared with the EPR, while the proportion of colloidal protein-like DOM in the >20 nm size range was slightly larger in the MR compared with the EPR. These features are consistent with differences in land use, hydrological conditions, and water residence time between the two river basins, with more autochthonous DOM in MR waters. In the SLB estuary, different DOM components demonstrated different mixing behaviors. The abundance of colloidal chromophoric DOM decreased with increasing salinity and showed evident removal during estuarine mixing even though the bulk DOM appeared to be conservative. In contrast, colloidal humic-like DOM behaved conservatively inside SLB and during laboratory mixing experiments. The ratio of colloidal protein-like to humic-like DOM generally increased with increasing salinity, consistent with increasing autochthonous protein-like DOM and removal of terrestrially-derived humic-like DOM in estuarine and coastal waters. Similar mixing behavior for the bulk DOM and colloids was observed in short-term laboratory mixing experiments, suggesting that physicochemical processes are the major controlling factor for colloidal removal in the estuary. For the first time, this study showed direct evidence of contrasting estuarine mixing behavior for different size fractions of optically active colloidal DOM.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP