Geology topics

Peter J. Hernes

Publications and source records attributed to Peter J. Hernes.

17 recordsLinked to original sources

USGS2023

Water-soluble organic carbon release from mineral soils and sediments in an irrigated agricultural system

Water interactions with soil and vegetation are greatly altered in agricultural watersheds compared to natural landscapes, which impacts sources and fates of organic carbon (OC). While mineral soil horizons in natural ecosystems primarily act as filters for dissolved organic carbon (DOC) leached from organic surface horizons, tilled soils largely lack an organic horizon and their mineral horizons therefore act as a source for both DOC and sediment to surface waters. Irrigated watersheds highlight this difference, as DOC and total suspended sediment (TSS) concentrations simultaneously increase during the low-discharge irrigation season, suggesting that sediment-associated OC may constitute a significant source of DOC. While water-soluble OC (WSOC) from sediments and soils has been found to be compositionally similar to stream DOC, these contributions remain poorly quantified in agricultural streams. To address this, we conducted abiotic solubilization experiments using sediments (suspended and bed) and soils from an irrigated agricultural watershed in northern California, USA. Sediments (R 2 > 0.99) and soils (0.74 < R 2 < 0.89) displayed linear solubilization behaviors over the range of concentrations tested. Suspended sediment from the irrigation season exhibited the largest solubilization efficiency (10.9 ± 1.6% TOC sediment solubilized) and potential (1.79 ± 0.26 mg WSOC g −1 dry sediment), followed by suspended sediment from a winter storm, then bed sediment and soils. Successive solubilization experiments increased the total release of WSOC by ∼50%, but most (88–97%) of the solid-phase OC remained insoluble in water. Using these solubilization potential estimates and measured TSS concentrations, we estimated that WSOC from suspended sediment in streams represented 4–7% of the annual DOC export from the watershed. However, field sediment export is much higher than what is represented by suspended sediment in the water column, therefore field-scale contributions from sediments could be much higher than estimated.

California↗

USGS2020

Vegetation vs. anoxic controls on degradation of plant litter in a restored wetland

The ability of wetlands to accrete organic matter in response to rising sea level is a key to landscape resilience, especially in light of reduced sediment availability consequent to dam construction and channelization. This study examined the degradation of cattail ( Typha spp.) and tule ( Schoenoplectus acutus ) litters in restored wetlands through the lens of lignin, a major structural biopolymer in vascular plants with degradation characteristics very sensitive to oxic versus anoxic conditions. A series of litterbags were deployed during the first 10 years after flooding of Deep (55 cm) and Shallow (25 cm) restored wetlands. As emergent marsh vegetation spread through the maturing wetlands, anoxic conditions were more prevalent and overall degradation rates of litter in litterbags were lower. In later experiments in the maturing wetlands, lignin was progressively enriched in litter as evidenced by carbon-normalized yields (Λ 8 ) that increased in tule starting materials from 6.3 to 7.1 mg 100 mgOC –1 to as high as 9.9 mg 100 mgOC –1 , and in cattail starting materials from 5.9 to 7.0 mg 100 mgOC –1 to as high as 10.9 mg 100 mgOC –1 . However, in an experiment initiated soon after the restored wetlands were constructed, Λ 8 in tule litter decreased from 6.8 to 3.6 mg 100 mgOC –1 , highlighting the prevalence of initial oxic conditions. With the exception of the early oxic conditions for tule, there was an overall trend of decreasing lignin acid-to-aldehyde ratios with litter degradation, which runs counter to most studies in the literature. We hypothesize that this reflects the utilization of more oxygen-rich lignin components as electron acceptors in redox reactions. No consistent differences were observed in degradation patterns between the Shallow and Deep wetlands. There were distinct differences in lignin degradation in cattail (more resistant) versus tule (less resistant), which indicates that although anoxia may be the dominant control on organic matter accretion in wetlands, specific types of vegetation in restored or constructed wetlands affects organic matter preservation, and hence accretion. Thus, selective management of predominant species in wetlands may prove important for the ability of wetlands to maintain emergent vegetation during sea level rise and to preserve the overall stability of wetland soils.

California↗

USGS2020

Reassessing particulate organic carbon dynamics in the highly disturbed San Francisco Bay Estuary

Environmental research has been shifting toward a new normal in which a primary focus is to capture change that may be accelerating. In this study, we collected particulate samples in the northern San Francisco Bay Estuary (SFBE) in the fall of 2011 through the spring of 2012 in order to assess vascular plant contributions across both time and space and to compare our findings with a similar set of samples from 1990 to 1992. Across the ∼20-year span, we detected (1) decreasing C:N a ratios (averages ± SD of 12.5 ± 2.5 vs. 8.8 ± 1.4, significant t -test with p < 0.0001); (2) distinct shifts in chlorophyll vs. salinity, with higher chlorophyll concentrations shifting toward freshwater; and (3) greater relative proportions of vascular plant carbon that also appears less degraded (as indicated by lignin measurements) shifting from freshwater toward higher salinities. Lignin compositional data (syringyl:vanillyl and cinnamyl:vanillyl) suggest that increased lignin content in the more saline samples could be derived from wetland materials, while a two-endmember mixing model indicates that a significant portion of the particulate organic carbon (POC) in the western sites (50–60% as an upper bound, 13–15% as a lower bound) could be wetland-derived. This has potential implications for the lower food web, given recent work that demonstrates selective feeding by copepods on wetland detrital material in the northern SFBE. The latter has ramifications for proposed wetland restoration within the SFBE and Sacramento River/San Joaquin River Delta system, namely, that restored wetlands could confer important benefits toward the food web. Equally important is to prioritize continued monitoring of particulate organic matter cycling in the SFBE system to make sure that changing conditions are accounted for in any management decision.

California↗

USGS2020

Organic matter integration, overprinting, and the relative fraction of optically active organic carbon in a human-impacted watershed

Rivers continually integrate terrestrial organic matter (OM) into their waters, in a process that transfers 1.9 Pg C yr –1 as the primary linkage between oceanic and terrestrial carbon cycles. Yet rivers are not simple, conservative OM integrators. Patchy local land uses (wetlands, bogs, agriculture) release OM that can disproportionately alter river biogeochemistry and overprint upstream carbon. These releases are quantifiable at the plot scale but remain unpredictable across river reaches and watersheds, critically inhibiting our ability to scale up terrestrial-aquatic linkages to regional/global carbon cycling models. We evaluated OM overprinting distance along a human-influenced watershed to quantify river integration of terrestrial OM and to bridge the quantification gap between habitats and waterway biogeochemistry. We investigated changes in dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition (lignin phenols, fluorescence excitation-emission spectra using parallel factor analysis [PARAFAC], and the relative fraction of optically active DOM [EEM DOC ]). DOC concentrations increased continually ( p < 0.001) downstream, from median 1.0 mg L –1 at 30 km (headwaters) to 3.3 mg L –1 at the river mouth. This rate of increase corresponded to a DOC overprinting distance—the longitudinal distance over which DOC concentrations double—of 13 km. Mainstem DOC overprinting distance ranged from 8 km (winter, rainy season) to 21 km (summer, dry season with irrigation), highlighting stronger overprinting during increased hydraulic connectivity. Stronger overprinting also correlated to higher EEM DOC ( p < 0.001). Overprinting distance effectively quantifies river integration of DOM along the terrestrial-aquatic interface, helping to refine bottom-up carbon cycle estimates, inform upscaling of site-specific fluxes, and to track land use and climate influence on river biogeochemistry.

California↗

USGS2020

Trihalomethane precursors: Land use hot spots, persistence during transport, and management options

To meet drinking water regulations, rather than investing in costly treatment plant operations, managers can look for ways to improve source water quality; this requires understanding watershed sources and fates of constituents of concern. Trihalomethanes (THMs) are one of the major classes of regulated disinfection byproducts, formed when a specific fraction of the organic carbon pool—referred to as THM precursors—reacts with chorine and/or bromine during treatment. Understanding the source, fate, timing and duration of the organic compounds that react to form THMs will allow identification of targeted and effective management actions. In this study we evaluated THM precursor contributions from multiple land use categories and hydrologic contexts, including novel data for urban land uses that demonstrate strong potential to release water with high THM formation potential (THMFP; median 618 μg L −1 ): greater than storm runoff integrated across a mixed-use (1/3 natural, 2/3 agricultural) watershed (median 460 μg L −1 ), irrigation runoff from agricultural systems (357 μg L −1 ), or runoff from a natural forested (median 123 μg L −1 ) and shrubland/grassland (median 259 μg L −1 ) watersheds. While individual storm events released high THM precursor concentrations over short periods, dry season agricultural irrigation as well as urban landscapes have the potential to release water high in THM precursors for several months. Experimental bioassays and sampling along 333 miles of the California Aqueduct confirmed bioavailability and photooxidation potential of less than 10% for THM precursors, suggesting that rivers with residence times of days to weeks may act as THM precursor conduits, shuttling THM precursors from hundreds of miles away to drinking water intakes with minimal degradation. This finding has considerable implications for water managers, who may therefore consider THM precursor management strategies that target even sources located far upstream.

California↗

USGS2017

Dissolved organic matter compositional change and biolability during two storm runoff events in a small sgricultural watershed

Agricultural watersheds are globally pervasive, supporting fundamentally different organic matter source, composition, and concentration profiles in comparison to natural systems. Similar to natural systems, agricultural storm runoff exports large amounts of organic carbon from agricultural land into waterways. But intense management of upper soil layers, waterway channelization, wetland and riparian habitat removal, and postharvest vegetation removal promise to uniquely drive organic matter release to waterways. During a winter first flush and a subsequent storm event, this study investigated the influence of a small agricultural watershed on dissolved organic matter (DOM) source, composition, and biolability. Storm water discharge released strongly terrestrial yet biolabile (23 to 32%) dissolved organic carbon (DOC). Following a 21 day bioassay, a parallel factor analysis identified an 80% reduction in a protein-like (phenylpropyl) component (C2) that was previously correlated to lignin phenol concentration, and a 10% reduction in a humic-like, terrestrially sourced component (C4). Storm-driven releases tripled DOC concentration (from 2.8 to 8.7 mg L −1 ) during the first flush event in comparison to base flow and were terrestrially sourced, with an eightfold increase in vascular plant derived lignin phenols (23.0 to 185 μg L −1 ). As inferred from system hydrology, lignin composition, and nitrate as a groundwater tracer, an initial pulse of dilute water from the upstream watershed caused a counterclockwise DOC hysteresis loop. DOC concentrations peaked after 3.5 days, with the delay between peak discharge and peak DOC attributed to storm water hydrology and a period of initial water repellency of agricultural soils, which delayed DOM leaching.

California↗

USGS2017

Irrigation as a fuel pump to freshwater ecosystems

We generated a detailed time series of total dissolved hydrolyzable amino acids (DHAA) in a watershed dominated by irrigated agriculture in northern California, USA to investigate the roles of hydrologic and seasonal changes on the composition of dissolved organic matter (DOM). DHAA are sensitive indicators of the degradation state and reactivity of DOM. DHAA concentrations ranged from 0.55 to 9.96 μM (median 3.51 ± 1.80 μM), with expected peaks during high-discharge storms and unexpected high values throughout the low-discharge irrigation season. Overall, summer irrigation was a critical hydrologic regime for DOM cycling since it mobilized DOM similar in concentration and reactivity to DOM released during storms. Together, irrigation and storm flows exported DOM with (1) the largest DHAA contributions to the dissolved organic carbon and the dissolved organic nitrogen pools, (2) the largest proportion of basic amino acids, and (3) the lowest degradation extent based on multiple indices. In this highly disturbed terrestrial system, UV–vis absorbance did not correlate with DHAA concentrations, while classic interpretations of common amino acid indicators (e.g., proportion of basic amino acids, degradation index, percent of non-protein amino acids) were prone to conflicting characterizations of DOM reactivity. Therefore, a new parameter (processing ratio, PR) derived from individual amino acid concentrations was developed that demonstrated a strong potential for mechanistic-driven characterization of the extent of DOM diagenesis in freshwaters. Irrigated agriculture altered stream biogeochemistry by releasing a continuous supply of reactive DOM (lowest PR values), thereby providing an additional energy source to downstream ecosystems.

California↗

USGS2013

The role of irrigation runoff and winter rainfall on dissolved organic carbon loads in an agricultural watershed

We investigated the role of land use/land cover and agriculture practices on stream dissolved organic carbon (DOC) dynamics in the Willow Slough watershed (WSW) from 2006 to 2008. The 415 km 2 watershed in the northern Central Valley, California is covered by 31% of native vegetation and the remaining 69% of agricultural fields (primarily alfalfa, tomatoes, and rice). Stream discharge and weekly DOC concentrations were measured at eight nested subwatersheds to estimate the DOC loads and yields (loads/area) using the USGS developed stream load estimation model, LOADEST. Stream DOC concentrations peaked at 18.9 mg L −1 during summer irrigation in the subwatershed with the highest percentage of agricultural land use, demonstrating the strong influence of agricultural activities on summer DOC dynamics. These high concentrations contributed to DOC yields increasing up to 1.29 g m −2 during the 6 month period of intensive agricultural activity. The high DOC yields from the most agricultural subwatershed during the summer irrigation period was similar throughout the study, suggesting that summer DOC loads from irrigation runoff would not change significantly in the absence of major changes in crops or irrigation practices. In contrast, annual DOC yields varied from 0.89 to 1.68 g m −2 yr −1 for the most agricultural watershed due to differences in winter precipitation. This suggests that variability in the annual DOC yields will be largely determined by the winter precipitation, which can vary significantly from year to year. Changes in precipitation patterns and intensities as well as agricultural practices have potential to considerably alter the DOC dynamics.

California↗

USGS2013

DOM composition in an agricultural watershed: assessing patterns and variability in the context of spatial scales

Willow Slough, a seasonally irrigated agricultural watershed in the Sacramento River valley, California, was sampled synoptically in order to investigate the extent to which dissolved organic carbon (DOC) concentrations and compositions from throughout the catchment are represented at the mouth. DOC concentrations ranged from 1.8 to 13.9 mg L −1 , with the lowest values in headwater 1st and 2nd order streams, and the highest values associated with flood irrigation. Carbon-normalized vanillyl phenols varied from 0.05 to 0.67 mg 100 mg OC −1 (0.37 mean), indicative of considerable contributions from vascular plants. DOC concentrations and compositions at the mouth appear to be primarily influenced by land use (agriculture) in the lower reaches, and therefore very little of the headwater chemistry (1st and 2nd order streams) can be discerned from the chemistry at or near the mouth (3rd and 4th order streams), indicating the need for synoptic sampling to capture the breadth of organic carbon cycling within a catchment. Field sampling during irrigation showed the large impact that flood irrigation can have on DOC concentrations and compositions, likely a primary cause of significantly elevated Willow Slough DOC concentrations during the summer irrigation season. Optical proxies exhibited varying degrees of correlation with chemical measurements, with strongest relationships to DOC and dissolved lignin ( r 2 = 0.95 and 0.73, respectively) and weaker relationships to carbon-normalized lignin yields and C:V ( r 2 from 0.31 to 0.42). Demonstrating the importance of matching scale to processes, we found no relationship between dissolved lignin concentrations and total suspended sediments (TSS) across all sites, in contrast to the strong relationship observed in weekly samples at the mouth. As DOC concentrations and compositions at the mouth of Willow Slough are closely tied to anthropogenic activities within the catchment, future changes in land-use driven by climate change, water availability, and economic pressures on crop types will also bring about changes in the overall biogeochemistry.

California↗

USGS2012

Anthropogenic aerosols as a source of ancient dissolved organic matter in glaciers

Glacier-derived dissolved organic matter represents a quantitatively significant source of ancient, yet highly bioavailable carbon to downstream ecosystems. This finding runs counter to logical perceptions of age–reactivity relationships, in which the least reactive material withstands degradation the longest and is therefore the oldest. The remnants of ancient peatlands and forests overrun by glaciers have been invoked as the source of this organic matter. Here, we examine the radiocarbon age and chemical composition of dissolved organic matter in snow, glacier surface water, ice and glacier outflow samples from Alaska to determine the origin of the organic matter. Low levels of compounds derived from vascular plants indicate that the organic matter does not originate from forests or peatlands. Instead, we show that the organic matter on the surface of the glaciers is radiocarbon depleted, consistent with an anthropogenic aerosol source. Fluorescence spectrophotometry measurements reveal the presence of protein-like compounds of microbial or aerosol origin. In addition, ultrahigh-resolution mass spectrometry measurements document the presence of combustion products found in anthropogenic aerosols. Based on the presence of these compounds, we suggest that aerosols derived from fossil fuel burning are a source of pre-aged organic matter to glacier surfaces. Furthermore, we show that the molecular signature of the organic matter is conserved in snow, glacier water and outflow, suggesting that the anthropogenic carbon is exported relatively unchanged in glacier outflows.

Nature Geoscience↗

USGS2012

An initial investigation into the organic matter biogeochemistry of the Congo River

The Congo River, which drains pristine tropical forest and savannah and is the second largest exporter of terrestrial carbon to the ocean, was sampled in early 2008 to investigate organic matter (OM) dynamics in this historically understudied river basin. We examined the elemental (%OC, %N, C:N), isotopic (δ 13 C, Δ 14 C, δ 15 N) and biochemical composition (lignin phenols) of coarse particulate (>63 μm; CPOM) and fine particulate (0.7–63 μm; FPOM) OM and DOC, δ 13 C, Δ 14 C and lignin phenol composition with respect to dissolved OM (<0.7 μm; DOM) from five sites in the Congo River Basin. At all sample locations the organic carbon load was dominated by the dissolved phase (~82–89% of total organic carbon) and the total suspended sediment load was principally fine particulate material (~81–91% fine suspended sediment). Distinct compositional and isotopic differences were observed between all fractions. Congo CPOM, FPOM and DOM all originated from vegetation and soil inputs as evidenced by elemental, isotopic and lignin phenol data, however FPOM was derived from much older carbon pools (mean Δ 14 C = -62.2 ± -13.2&permil;, n = 5) compared to CPOM and DOM (mean Δ 14 C = 55.7 ± 30.6&permil;, n = 4 and 73.4 ± 16.1&permil;, n = 5 respectively). The modern radiocarbon ages for DOM belie a degraded lignin compositional signature (i.e. elevated acid:aldehyde ratios (Ad:Al) relative to CPOM and FPOM), and indicate that the application of OM degradation patterns derived from particulate phase studies to dissolved samples needs to be reassessed: these elevated ratios are likely attributable to fractionation processes during solubilization of plant material. The relatively low DOM carbon-normalized lignin yields (Λ8; 0.67–1.12 (mg(100 mg OC) -1 )) could also reflect fractionation processes, however, they have also been interpreted as an indication of significant microbial or algal sources of DOM. CPOM appears to be well preserved higher vascular plant material as evidenced by its modern radiocarbon age, elevated C:N (17.2–27.1) and Λ8 values (4.56–7.59 (mg(100 mg OC) -1 )). In relation to CPOM, the aged FPOM fraction (320–580 ybp 14 C ages) was comparatively degraded, as demonstrated by its nitrogen enrichment (C:N 11.4–14.3), lower Λ8 (2.80–4.31 (mg(100 mg OC) -1 )) and elevated lignin Ad:Al values similar to soil derived OM. In this study we observed little modification of the OM signature from sample sites near the cities of Brazzaville and Kinshasa to the head of the estuary (~350 km) highlighting the potential for future studies to assess seasonal and long-term OM dynamics from this logistically feasible location and derive relevant information with respect to OM exported to the Atlantic Ocean. The relative lack of OM data for the Congo River Basin highlights the importance of studies such as this for establishing baselines upon which to gauge future change.

Congo River↗

USGS2011

How reservoirs alter drinking water quality: Organic matter sources, sinks, and transformations

Within reservoirs, production, transformation, and loss of dissolved organic matter (DOM) occur simultaneously. While the balance between production and loss determines whether a reservoir is a net sink or source of DOM, changes in chemical composition are also important because they affect DOM reactivity with respect to disinfection by-product (DBP) formation. The composition of the DOM pool also provides insight into DOM sources and processing, which can inform reservoir management. We examined the concentration and composition of DOM in San Luis Reservoir, a large off-stream impoundment of the California State Water Project. We used a wide array of DOM chemical tracers including dissolved organic carbon (DOC) concentration, trihalomethane and haloacetic acid formation potentials (THMFP and HAAFP, respectively), absorbance properties, isotopic composition, lignin phenol content, and structural groupings determined by 13 C nuclear magnetic resonance (NMR). There were periods when the reservoir was a net source of DOC due to the predominance of algal production (summer), a net sink due to the predominance of degradation (fall–winter), and balanced between production and consumption (spring). Despite only moderate variation in bulk DOC concentration (3.0–3.6 mg C/L), changes in DOM composition indicated that terrestrial-derived material entering the reservoir was being degraded and replaced by aquatic-derived DOM produced within the reservoir. Substantial changes in the propensity of the DOM pool to form THMs and HAAs illustrate that the DBP precursor pool was not directly coupled to bulk DOC concentration and indicate that algal production is an important source of DBP precursors. Results suggest reservoirs have the potential to attenuate DOM amount and reactivity with respect to DBP precursors via degradative processes; however, these benefits can be decreased or even negated by the production of algal-derived DOM.

California↗

USGS2010

Comparison of XAD with other dissolved lignin isolation techniques and a compilation of analytical improvements for the analysis of lignin in aquatic settings

This manuscript highlights numerous incremental improvements in dissolved lignin measurements over the nearly three decades since CuO oxidation of lignin phenols was first adapted for environmental samples. Intercomparison of the recovery efficiency of three common lignin phenol concentration and isolation techniques, namely XAD, C 18 with both CH 3 OH (C 18 M) and CH 3 CN (C 18 A) used independently for priming and elution steps, and tangential flow filtration (TFF) for a range of aquatic samples including fresh, estuarine and marine waters, was undertaken. With freshwater samples XAD8-1, C 18 M and TFF were all observed to recover ca. 80–90% of the lignin phenols and showed no fractionation effects with respect to diagnostic lignin parameters. With estuarine and marine samples more lignin phenols were recovered with C 18 M and XAD8-1 than TFF because of the increased prevalence of low molecular weight lignin phenols in marine influenced samples. For marine systems, differences were also observed between diagnostic lignin parameters isolated via TFF vs. C 18 M and XAD8-1 as a result of the high molecular weight lignin phenols being less degraded than the bulk. Therefore, it is recommended for future studies of marine systems that only one technique is utilized for ease of intercomparison within studies. It is suggested that for studies solely aimed at recovering bulk dissolved lignin in marine environments that C 18 M and XAD8-1 appear to be more suitable than TFF as they recover more lignin. Our results highlight that, for freshwater samples, all three common lignin phenol concentration and isolation techniques are comparable to whole water concentrated by rotary evaporation (i.e. not isolated) but, that for marine systems, the choice of concentration and isolation techniques needs to be taken into consideration with respect to both lignin concentration and diagnostic parameters. Finally, as the study highlights XAD8-1 to be a suitable method for the isolation of dissolved lignin phenols from aquatic systems (statistically indistinguishable from C 18 M, P < 0.1), lignin data representative of whole waters can be produced for IHSS reference materials or other XAD sample archives.

Organic Geochemistry↗

USGS2010

Microbial degradation of plant leachate alters lignin phenols and trihalomethane precursors

Although the importance of vascular plant-derived dissolved organic carbon (DOC) in freshwater systems has been studied, the role of leached DOC as precursors of disinfection byproducts (DBPs) during drinking water treatment is not well known. Here we measured the propensity of leachates from four crops and four aquatic macrophytes to form trihalomethanes (THMs)—a regulated class of DBPs—before and after 21 d of microbial degradation. We also measured lignin phenol content and specific UV absorbance (SUVA 254 ) to test the assumption that aromatic compounds from vascular plants are resistant to microbial degradation and readily form DBPs. Leaching solubilized 9 to 26% of total plant carbon, which formed 1.93 to 6.72 mmol THM mol C -1 However, leachate DOC concentrations decreased by 85 to 92% over the 21-d incubation, with a concomitant decrease of 67 to 92% in total THM formation potential. Carbon-normalized THM yields in the residual DOC pool increased by 2.5 times on average, consistent with the preferential uptake of nonprecursor material. Lignin phenol concentrations decreased by 64 to 96% over 21 d, but a lack of correlation between lignin content and THM yields or SUVA 254 suggested that lignin-derived compounds are not the source of increased THM precursor yields in the residual DOC pool. Our results indicate that microbial carbon utilization alters THM precursors in ecosystems with direct plant leaching, but more work is needed to identify the specific dissolved organic matter components with a greater propensity to form DBPs and affect watershed management, drinking water quality, and human health.

Journal of Environmental Quality↗

USGS2009

Fluorescence-based proxies for lignin in freshwater dissolved organic matter

Lignin phenols have proven to be powerful biomarkers in environmental studies; however, the complexity of lignin analysis limits the number of samples and thus spatial and temporal resolution in any given study. In contrast, spectrophotometric characterization of dissolved organic matter (DOM) is rapid, noninvasive, relatively inexpensive, requires small sample volumes, and can even be measured in situ to capture fine-scale temporal and spatial detail of DOM cycling. Here we present a series of cross-validated Partial Least Squares models that use fluorescence properties of DOM to explain up to 91% of lignin compositional and concentration variability in samples collected seasonally over 2 years in the Sacramento River/San Joaquin River Delta in California, United States. These models were subsequently used to predict lignin composition and concentration from fluorescence measurements collected during a diurnal study in the San Joaquin River. While modeled lignin composition remained largely unchanged over the diurnal cycle, changes in modeled lignin concentrations were much greater than expected and indicate that the sensitivity of fluorescence-based proxies for lignin may prove invaluable as a tool for selecting the most informative samples for detailed lignin characterization. With adequate calibration, similar models could be used to significantly expand our ability to study sources and processing of DOM in complex surface water systems.

Journal of Geophysical Research G: Biogeosciences↗

USGS2008

Seasonal and spatial variability in dissolved organic matter quantity and composition from the Yukon River basin, Alaska

[1] The seasonal and spatial variability of dissolved organic matter (DOM) quantity and chemical composition were investigated in the Yukon River basin of Alaska, United States, and northwestern Canada. Dissolved organic carbon (DOC), chromophoric DOM (CDOM), and dissolved lignin phenols were measured across a range of source waters and the seasonal hydrograph. Strong relationships were determined between CDOM and both DOC and lignin phenols, highlighting the potential for deriving detailed spatial and temporal distributions of DOM composition from CDOM monitoring. Maximum concentrations of measured parameters were observed during the spring flush, when DOM had a remarkably high content of aromatic vascular plant material derived from surface soil and litter layers. A larger portion of riverine DOM was attributed to vascular plant sources than previously believed by utilizing representative vegetation leachates and a soil pore water as end‐members. In combination with recent studies highlighting export of young, labile DOM during the spring flush in northern high‐latitude river systems, our results suggest riverine DOM is less degraded and more labile than previously thought with clear ramifications for its biomineralization or photo‐oxidation in marine environments.

Global Biogeochemical Cycles↗

USGS2007

Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L -1 within the Sacramento River to 39.9 mg L -1 at the outfall from an island drain (median 3.0 mg L -1 ), while lignin concentrations ranged from 3.0 μL -1 within the Sacramento River to 111 μL -1 at the outfall from an island drain (median 11.6 μL -1 ). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC) -1 at an island drain to 0.84 mg (100 mg OC) -1 for a wetland (median 0.36 mg (100 mg OC) -1 ), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of localized landscape features, and is also the first to indicate a significant negative correlation between lignin and DOC bioavailability within environmental samples. Based upon observed trends: (1) Delta features exhibit significant spatial variability in organic chemical composition, and (2) localized Delta features appear to exert strong controls on terrigenous DOC as it passes through the Delta and is exported into the Pacific Ocean.

California↗