[Show abstract][Hide abstract] ABSTRACT: This study focused on the importance of the colmation layer in the removal of cyanobacteria, viruses, and dissolved organic carbon (DOC) during natural bank filtration. Injection-and-recovery studies were performed at two shallow (0.5 m deep), sandy, near-shore sites at the southern end of Ashumet Pond, a waste-impacted, kettle pond on Cape Cod, MA, that is subject to periodic blooms of cyanobacteria and continuously recharges a sole-source drinking-water aquifer. The experiment involved assessing the transport behaviors of bromide (conservative tracer), sp. IU625 (cyanobacterium, 2.6 ± 0.2 µm), AS-1 (tailed cyanophage, 110 nm long), MS2 (coliphage, 26 nm diameter), and carboxylate-modified microspheres (1.7 µm diameter) introduced to the colmation layer using a bag-and-barrel (Lee-type) seepage meter. The injectate constituents were tracked as they were advected across the pond water-groundwater interface and through the underlying aquifer sediments under natural-gradient conditions past push-point samplers placed at ∼30-cm intervals along a 1.2-m-long, diagonally downward flow path. More than 99% of the microspheres, IU625, MS2, AS-1, and ∼44% of the pond DOC were removed in the colmation layer (upper 25 cm of poorly sorted bottom sediments) at two test locations characterized by dissimilar seepage rates (1.7 vs. 0.26 m d). Retention profiles in recovered core material indicated that >82% of the attached IU625 were in the top 3 cm of bottom sediments. The colmation layer was also responsible for rapid changes in the character of the DOC and was more effective (by three orders of magnitude) at removing microspheres than was the underlying 20-cm-thick segment of sediment.
[Show abstract][Hide abstract] ABSTRACT: Sources, abundance, isotopic compositions, and export fluxes of dissolved inorganic carbon (DIC), dissolved and colloidal organic carbon (DOC and COC), and particulate organic carbon (POC), and their response to hydrologic regimes were examined through monthly sampling from the Lower Mississippi River during 2006–2008. DIC was the most abundant carbon species, followed by POC and DOC. Concentration and δ13C of DIC decreased with increasing river discharge while those of DOC remained fairly stable. COC comprised 61 ± 3% of the bulk DOC with similar δ13C abundances but higher percentages of hydrophobic organic acids than DOC, suggesting its aromatic and diagenetically younger status. POC showed peak concentrations during medium flooding events and at the rising limb of large flooding events. While δ13C-POC increased, δ15N of particulate nitrogen decreased with increasing discharge. Overall, the differences in δ13C between DOC or DIC and POC show an inverse correlation with river discharge. The higher input of soil organic matter and respired CO2 during wet seasons was likely the main driver for the convergence of δ13C between DIC and DOC or POC, whereas enhanced in situ primary production and respiration during dry seasons might be responsible for their isotopic divergence. Carbon export fluxes from the Mississippi River were estimated to be 13.6 Tg-C y−1 for DIC, 1.88 Tg-C y−1 for DOC, and 2.30 Tg-C y−1 for POC during 2006–2008. The discharge-normalized DIC yield decreased during wet seasons while those of POC and DOC increased and remained constant, respectively, implying variable responses in carbon export to the increasing discharge.
[Show abstract][Hide abstract] ABSTRACT: The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg-C L(-1)) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles.
[Show abstract][Hide abstract] ABSTRACT: Methylmercury is the environmental form of neurotoxic mercury that is biomagnified in the food chain. Methylation rates are reduced when the metal is sequestered in crystalline mercury sulfides or bound to thiol groups in macromolecular natural organic matter. Mercury sulfide minerals are known to nucleate in anoxic zones, by reaction of the thiol-bound mercury with biogenic sulfide, but not in oxic environments. We present experimental evidence that mercury sulfide forms from thiol-bound mercury alone in aqueous dark systems in contact with air. The maximum amount of nanoparticulate mercury sulfide relative to thiol-bound mercury obtained by reacting dissolved mercury and soil organic matter matches that detected in the organic horizon of a contaminated soil situated downstream from Oak Ridge, Tennessee, in the USA. The nearly identical ratios of the two forms of mercury in field and experimental systems suggest a common reaction mechanism for nucleating the mineral. We identified a chemical reaction mechanism that is thermodynamically favorable in which thiol-bound mercury polymerizes to mercury-sulfur clusters. The clusters form by elimination of sulfur from the thiol complexes via breaking of mercury-sulfur bonds as in an alkylation reaction. Addition of sulfide is not required. This nucleation mechanism provides one explanation for how mercury may be immobilized, and eventually sequestered, in oxygenated surface environments.
[Show abstract][Hide abstract] ABSTRACT: Surface waters play a potentially important role in the global carbon balance. Dissolved organic carbon (DOC) fluxes are a major transfer of terrestrial carbon to river systems, and the fate of DOC in aquatic systems is poorly constrained. We used a unique combination of spatially distributed sampling of three DOC fractions throughout a river network and modeling to quantify the net removal of terrestrial DOC during a summer base flow period. We found that aquatic reactivity of terrestrial DOC leading to net loss is low, closer to conservative chloride than to reactive nitrogen. Net removal occurred mainly from the hydrophobic organic acid fraction, while hydrophilic and transphilic acids showed no net change, indicating that partitioning of bulk DOC into different fractions is critical for understanding terrestrial DOC removal. These findings suggest that river systems may have only a modest ability to alter the amounts of terrestrial DOC delivered to coastal zones.
[Show abstract][Hide abstract] ABSTRACT: 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.
[Show abstract][Hide abstract] ABSTRACT: The residence time of ice in permafrost is an indicator of past climate history, and of the resilience and vulnerability of high-latitude ecosystems to global change. Development of geochemical indicators of ground-ice residence times in permafrost will advance understanding of the circumstances and evidence of permafrost formation, preservation, and thaw in response to climate warming and other disturbance. We used uranium isotopes to evaluate the residence time of segregated ground ice from ice-rich loess permafrost cores in central Alaska. Activity ratios of 234U vs. 238U (234U/238U) in water from thawed core sections ranged between 1.163 and 1.904 due to contact of ice and associated liquid water with mineral surfaces over time. Measured (234U/238U) values in ground ice showed an overall increase with depth in a series of five neighboring cores up to 21 m deep. This is consistent with increasing residence time of ice with depth as a result of accumulation of loess over time, as well as characteristic ice morphologies, high segregated ice content, and wedge ice, all of which support an interpretation of syngenetic permafrost formation associated with loess deposition. At the same time, stratigraphic evidence indicates some past sediment redistribution and possibly shallow thaw among cores, with local mixing of aged thaw waters. Using measures of surface area and a leaching experiment to determine U distribution, a geometric model of (234U/238U) evolution suggests mean ages of up to ∼200 ky BP in the deepest core, with estimated uncertainties of up to an order of magnitude. Evidence of secondary coatings on loess grains with elevated (234U/238U) values and U concentrations suggests that refinement of the geometric model to account for weathering processes is needed to reduce uncertainty. We suggest that in this area of deep ice-rich loess permafrost, ice bodies have been preserved from the last glacial period (10-100 ky BP), despite subsequent fluctuations in climate, fire disturbance and vegetation. Radiocarbon (14C) analysis of dissolved organic carbon (DOC) in thaw waters supports ages greater than ∼40 ky BP below 10 m. DOC concentrations in thaw waters increased with depth to maxima of >1000 ppm, despite little change in ice content or cryostructures. These relations suggest time-dependent production of old DOC that will be released upon permafrost thaw at a rate that is mediated by sediment transport, among other factors.
[Show abstract][Hide abstract] ABSTRACT: Recent warming at high latitudes has accelerated permafrost thaw, which can modify soil carbon dynamics and watershed hydrology. The flux and composition of dissolved organic matter (DOM) from soils to rivers is sensitive to permafrost configuration and its impact on subsurface hydrology and groundwater discharge. Here, we evaluate the utility of DOM composition and age as a tool for detecting permafrost thaw in three rivers (Beaver, Birch and Hess Creeks) within the discontinuous permafrost zone of interior Alaska. We observed strong temporal controls on Δ14C content of hydrophobic acid isolates (Δ14C-HPOA) across all rivers, with the most enriched values occurring during spring snowmelt (75 ± 8 ‰) and most depleted during winter flow (−21 ± 8 ‰). Radiocarbon ages of winter flow samples ranged from 35 to 445 y BP, closely tracking estimated median baseflow travel times for this region (335 y). During spring snowmelt, young DOM was composed of highly aromatic, high molecular-weight compounds, whereas older DOM of winter flow had lower aromaticity and molecular weight. We observed a significant correlation between Δ14C-HPOA and UV absorbance coefficient at 254 nm (α254) across all study rivers. Using α254 as an optical indicator for Δ14C-HPOA, we also observed a long-term decline in α254 during maximum annual thaw depth over the last decade at the Hess Creek study site. These findings suggest a shift in watershed hydrology associated with increasing active layer thickness. Further development of DOM optical indicators may serve as a novel and inexpensive tool for detecting permafrost degradation in northern watersheds.
[Show abstract][Hide abstract] ABSTRACT: Iron is a source of interference in the spectroscopic analysis of dissolved organic matter (DOM); however, its effects on commonly-employed ultraviolet and visible (UV-Vis) light adsorption and fluorescence measurements are poorly defined. Here, we describe the effects of iron(II) and iron(III) on the UV-Vis absorption and fluorescence of solutions containing two DOM fractions and two surface water samples. In each case, regardless of DOM composition, UV-Vis absorption increased linearly with increasing iron(III). Correction factors were derived using iron(III) absorption coefficients determined at wavelengths commonly used to characterize DOM. Iron(III) addition increased specific UV absorbances (SUVA) and decreased the absorption ratios (E2:E3) and spectral slope ratios (SR) of DOM samples. Both iron(II) and iron(III) quenched DOM fluorescence at pH 6.7. The degree and region of fluorescence quenching varied with the iron:DOC concentration ratio, DOM composition, and pH. Regions of the fluorescence spectra associated with greater DOM conjugation were more susceptible to iron quenching, and DOM fluorescence indices were sensitive to the presence of both forms of iron. Analyses of the excitation-emission matrices using a 7- and 13-component parallel factor analysis (PARAFAC) model showed low PARAFAC sensitivity to iron addition.
[Show abstract][Hide abstract] ABSTRACT: Responses of near-surface permafrost and glacial ice to climate change are of particular significance for understanding long term effects on global carbon cycling and carbon export by high-latitude northern rivers. Here we report Δ14C -dissolved organic carbon (DOC) values and dissolved organic matter optical data for the Yukon River, 15 tributaries of the Yukon River, glacial meltwater, and groundwater and soil water endmember sources draining to the Yukon River, with the goal of assessing mobilization of aged DOC within the watershed. Ancient DOC was associated with glacial meltwater and groundwater sources. In contrast, DOC from watersheds dominated by peat soils and underlain by permafrost was typically enriched in Δ14C indicating that degradation of ancient carbon stores is currently not occurring at large enough scales to quantitatively influence bulk DOC exports from those landscapes. On an annual basis, DOC exported was predominantly modern during the spring period throughout the Yukon River basin, and became older through summer-fall and winter periods, suggesting that contributions of older DOC from soils, glacial meltwaters and groundwater are significant during these months. Our data indicate that rapidly receding glaciers and increasing groundwater inputs will likely result in greater contributions of older DOC in the Yukon River and its tributaries in coming decades.
[Show abstract][Hide abstract] ABSTRACT: Dissolved organic matter (DOM) was isolated from large volumes of deep (674 m) and surface (21 m) ocean water via reverse osmosis/electrodialysis (RO/ED) and two solid-phase extraction (SPE) methods (XAD-8/4 and PPL) at the Natural Energy Laboratory of Hawaii Authority (NELHA). By applying the three methods to common water samples, the efficiencies of XAD, PPL and RO/ED DOM isolation were compared. XAD recovered 42% of dissolved organic carbon (DOC) from deep water (25% with XAD-8; 17% with XAD-4) and 30% from surface water (16% with XAD-8; 14% with XAD-4). PPL recovered 61 ± 3% of DOC from deep water and 61% from surface water. RO/ED recovered 82 ± 3% of DOC from deep water, 14 ± 3% of which was recovered in a sodium hydroxide rinse, and 75 ± 5% of DOC from surface water, with 12 ± 2% in the sodium hydroxide rinse. The highest recoveries of all were achieved by the sequential isolation of DOC, first with PPL and then via RO/ED. This combined technique recovered 98% of DOC from a deep water sample and 101% of DOC from a surface water sample. In total, 1.9, 10.3 and 1.6 g-C of DOC were collected via XAD, PPL and RO/ED, respectively. Rates of DOC recovery using the XAD, PPL and RO/ED methods were 10, 33 and 10 mg-C hr- 1, respectively. Based upon C/N ratios XAD was heavily C-enriched compared water column DOM, whereas RO/ED and PPL➔RO/ED isolate C/N values were most representative of the original DOM. All techniques are suitable for the isolation of large amounts of DOM with purities suitable for most advanced analytical techniques. Coupling PPL and RO/ED techniques may provide substantial progress in the search for a method to quantitatively isolate oceanic DOC, bringing the entirety of the DOM pool within the marine chemist’s analytical window.
[Show abstract][Hide abstract] ABSTRACT: Southeastern Alaska is a remote coastal-maritime ecosystem that is experiencing increased deposition of mercury (Hg) as well as rapid glacier loss. Here we present the results of the first reported survey of total and methyl Hg (MeHg) concentrations in regional streams and biota. Overall, streams draining large wetland areas had higher Hg concentrations in water, mayflies, and juvenile salmon than those from glacially-influenced or recently deglaciated watersheds. Filtered MeHg was positively correlated with wetland abundance. Aqueous Hg occurred predominantly in the particulate fraction of glacier streams but in the filtered fraction of wetland-rich streams. Colonization by anadromous salmon in both glacier and wetland-rich streams may be contributing additional marine-derived Hg. The spatial distribution of Hg in the range of streams presented here shows that watersheds are variably, yet fairly predictably, sensitive to atmospheric and marine inputs of Hg.
[Show abstract][Hide abstract] ABSTRACT: Understanding the processes controlling the transfer and chemical composition of
dissolved organic carbon (DOC) in freshwater systems is crucial to understanding the
carbon cycle and the effects of DOC on water quality. Previous studies have identified
watershed-scale controls on bulk DOC flux and concentration among small basins but
fewer studies have explored controls among large basins or simultaneously considered the
chemical composition of DOC. Because the chemical character of DOC drives riverine
biogeochemical processes such as metabolism and photodegradation, accounting for
chemical character in watershed-scale studies will improve the way bulk DOC variability
in rivers is interpreted. We analyzed DOC quantity and chemical character near the mouths
of 17 large North American rivers, primarily between 2008 and 2010, and identified
watershed characteristics that controlled variability. We quantified DOC chemical
character using both specific ultraviolet absorbance at 254 nm (SUVA254) and XAD-resin
fractionation. Mean DOC concentration ranged from 2.1 to 47 mg C L�1 and mean
SUVA254 ranged from 1.3 to 4.7 Lmg C�1m�1.We found a significant positive correlation
between basin wetland cover and both bulk DOC concentration (R2 = 0.78; p<0.0001) and
SUVA254 (R2 = 0.91; p<0.0001), while other land use characteristics were not correlated.
The strong wetland relationship with bulk DOC concentration is similar to that found by
others in small headwater catchments. However, two watersheds with extremely long
surface water residence times, the Colorado and St. Lawrence, diverged from this wetland
relationship. These results suggest that the role of riverine processes in altering the
terrestrial DOC signal at the annual scale was minimal except in river systems with long
surface water residence times. However, synoptic DOC sampling of both quantity and
character throughout river networks will be needed to more rigorously test this finding. The
inclusion of DOC chemical character will be vital to achieving a more complete
understanding of bulk DOC dynamics in large river systems.
[Show abstract][Hide abstract] ABSTRACT: Dissolved organic matter (DOM) is a key component of fate and transport models for most metals, including mercury (Hg). Utilizing a suite of diverse DOM isolates, we demonstrated that DOM character, in addition to concentration, influences inorganic Hg (Hg(II)i) bioavailability to Hg-methylating bacteria. Using a model Hg-methylating bacterium, Desulfovibrio desulfuricans ND132, we evaluated Hg-DOM-sulfide bioavailability in washed-cell assays at environmentally relevant Hg/DOM ratios (~1-8 ng Hg/mg C) and sulfide concentrations (1-1000 µM). All tested DOM isolates significantly enhanced Hg methylation above DOM-free controls (from ~2 to >20-fold for 20 mg C/L DOM solutions), but high molecular weight/highly aromatic DOM isolates and/or those with high sulfur content were particularly effective at enhancing Hg methylation. Because these experiments were conducted under conditions of predicted super-saturation with respect to metacinnabar (β-HgS(s)), we attribute the DOM-dependent enhancement of Hg(II)i bioavailability to steric and specific chemical (e.g., DOM thiols) inhibition of β-HgS(s) growth and aggregation by DOM. Experiments examining the role of DOM across a wide sulfide gradient revealed that DOM only enhances Hg methylation under fairly low sulfide conditions (< ~30 µM), conditions that favor HgS nanoparticle/cluster formation relative to dissolved HgS species. <sup></sub><sub><sub><sub>
[Show abstract][Hide abstract] ABSTRACT: 1] Chromophoric dissolved organic matter (CDOM) fluxes and yields from 15 major U.S. rivers draining an assortment of terrestrial biomes are presented. A robust relationship between CDOM and dissolved organic carbon (DOC) loads is established (e.g., a 350 versus DOC; r 2 = 0.96, p < 0.001). Calculated CDOM yields are also correlated to watershed percent wetland (e.g. a 350 ; r 2 = 0.81, p < 0.001) providing a method for the estimation of CDOM export from ungauged watersheds. A large variation in CDOM yields was found across the rivers. The two rivers in the north-eastern U.S. (Androscoggin and Penobscot), the Edisto draining into the South Atlantic Bight, and some rivers draining into the Gulf of Mexico (Atchafalaya and Mobile) exhibit the highest CDOM yields, linked to extensive wetlands in these watersheds. If the Edisto CDOM yield is representative of other rivers draining into the South Atlantic Bight, this would result in a CDOM load equivalent to that of the Mississippi from a region of approximately 10% of the Mississippi watershed, indicating the importance of certain regions with respect to the role of terrigenous CDOM in ocean color budgets.
Geophysical Research Letters 04/2013; 40(8):1575-1579. DOI:10.1002/grl.50357 · 4.20 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Water samples were collected from six small rivers in the Yukon River basin in central Alaska to examine the role of colloids and organic matter in the transport of trace elements in Northern high latitude watersheds influenced by permafrost. Concentrations of dissolved organic carbon (DOC), selected elements (Al, Si, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Ba, Pb, U), and UV-absorbance spectra were measured in 0.45 μm filtered samples. ‘Nanocolloidal size distributions’ (0.5–40 nm, hydrodynamic diameter) of humic-type and chromophoric dissolved organic matter (CDOM), Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pb were determined by on-line coupling of flow field-flow fractionation (FFF) to detectors including UV-absorbance, fluorescence, and ICP-MS. Total dissolved and nanocolloidal concentrations of the elements varied considerably between the rivers and between spring flood and late summer base flow. Data on specific UV-absorbance (SUVA), spectral slopes, and the nanocolloidal fraction of the UV-absorbance indicated a decrease in aromaticity and size of CDOM from spring flood to late summer. The nanocolloidal size distributions indicated the presence of different ‘components’ of nanocolloids. ‘Fulvic-rich nanocolloids’ had a hydrodynamic diameter of 0.5–3 nm throughout the sampling season; ‘organic/iron-rich nanocolloids’ occurred in the <8 nm size range during the spring flood; whereas ‘iron-rich nanocolloids’ formed a discrete 4–40 nm components during summer base flow. Mn, Co, Ni, Cu and Zn were distributed between the nanocolloid components depending on the stability constant of the metal (+II)–organic complexes, while stronger association of Cr to the iron-rich nanocolloids was attributed to the higher oxidation states of Cr (+III or +IV). Changes in total dissolved element concentrations, size and composition of CDOM, and occurrence and size of organic/iron and iron-rich nanocolloids were related to variations in their sources from either the upper organic-rich soil or the deeper mineral layer, depending on seasonal variations in hydrological flow patterns and permafrost dynamics.