Representing the function and sensitivity of coastal interfaces in Earth system models.

Between the land and ocean, diverse coastal ecosystems transform, store, and transport material. Across these interfaces, the dynamic exchange of energy and matter is driven by hydrological and hydrodynamic processes such as river and groundwater discharge, tides, waves, and storms. These dynamics regulate ecosystem functions and Earth's climate, yet global models lack representation of coastal processes and related feedbacks, impeding their predictions of coastal and global responses to change. Here, we assess existing coastal monitoring networks and regional models, existing challenges in these efforts, and recommend a path towards development of global models that more robustly reflect the coastal interface.

Sources, Ages, and Alteration of Organic Matter in Estuaries.

Understanding the processes influencing the sources and fate of organic matter (OM) in estuaries is important for quantifying the contributions of carbon from land and rivers to the global carbon budget of the coastal ocean. Estuaries are sites of high OM production and processing, and understanding biogeochemical processes within these regions is key to quantifying organic carbon (Corg) budgets at the land-ocean margin. These regions provide vital ecological services, including nutrient filtration and protection from floods and storm surge, and provide habitat and nursery areas for numerous commercially important species. Human activities have modified estuarine systems over time, resulting in changes in the production, respiration, burial, and export of Corg. Corg in estuaries is derived from aquatic, terrigenous, and anthropogenic sources, with each source exhibiting a spectrum of ages and lability. The complex source and age characteristics of Corg in estuaries complicate our ability to trace OM along the river-estuary-coastal ocean continuum. This review focuses on the application of organic biomarkers and compound-specific isotope analyses to estuarine environments and on how these tools have enhanced our ability to discern natural sources of OM, trace their incorporation into food webs, and enhance understanding of the fate of Corg within estuaries and their adjacent waters.

Biogenic polycyclic aromatic hydrocarbons in sediments of the San Joaquin River in California (USA), and current paradigms on their formation.

Biogenic perylene and higher plant pentacyclic triterpenoid-derived alkylated and partially aromatized tetra- and pentacyclic derivatives of chrysene (3,4,7-trimethyl- and 3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, THC) and picene (1,2,9-trimethyl- and 2,2,9-trimethyl-1,2,3,4-tetrahydropicene, THP) were two- to four-fold more abundant than pyrogenic PAH in two sediment cores from the San Joaquin River in Northern California (USA). In a core from Venice Cut (VC), located in the river, PAH concentrations varied little downcore and the whole-core PAH concentration (biogenics + pyrogenics) was 250.6 ± 73.7 ng g(-1) dw; biogenic PAH constituted 67 ± 4 % of total PAH. THC were 26 ± 9 % of total biogenic PAH, THP were 36 ± 7 %, and perylene was 38 ± 7 %. PAH distributions in a core from Franks Tract (FT), a former wetland that was converted to an agricultural tract in the late 1800s and flooded in 1938, were more variable. Surface sediments were dominated by pyrogenic PAH so that biogenic PAH were only ~30 % of total PAH. Deeper in the core, biogenic PAH constituted 60-93 % of total PAH; THC, THP and perylene were 31 ± 28 %, 24 ± 32 %, and 45 ± 36 % of biogenic PAH. At 100-103 cm depth, THP constituted 80 % of biogenic PAH and at 120-123 cm perylene was 95 % of biogenic PAH. Current concepts related to precursors and transformation processes responsible for the diagenetic generation of perylene and triterpenoid-derived PAH are discussed. Distributions of biogenic PAH in VC and FT sediments suggest that they may not form diagenetically within these sediments but rather might be delivered pre-formed from the river's watershed.

Use of ESI-FTICR-MS to Characterize Dissolved Organic Matter in Headwater Streams Draining Forest-Dominated and Pasture-Dominated Watersheds.

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proven to be a powerful technique revealing complexity and diversity of natural DOM molecules, but its application to DOM analysis in grazing-impacted agricultural systems remains scarce. In the present study, we presented a case study of using ESI-FTICR-MS in analyzing DOM from four headwater streams draining forest- or pasture-dominated watersheds in Virginia, USA. In all samples, most formulas were CHO compounds (71.8-87.9%), with other molecular series (CHOS, CHON, CHONS, and CHOP (N, S)) accounting for only minor fractions. All samples were dominated by molecules falling in the lignin-like region (H/C = 0.7-1.5, O/C = 0.1-0.67), suggesting the predominance of allochthonous, terrestrial plant-derived DOM. Relative to the two pasture streams, DOM formulas in the two forest streams were more similar, based on Jaccard similarity coefficients and nonmetric multidimensional scaling calculated from Bray-Curtis distance. Formulas from the pasture streams were characterized by lower proportions of aromatic formulas and lower unsaturation, suggesting that the allochthonous versus autochthonous contributions of organic matter to streams were modified by pasture land use. The number of condensed aromatic structures (CAS) was higher for the forest streams, which is possibly due to the controlled burning in the forest-dominated watersheds and suggests that black carbon was mobilized from soils to streams. During 15-day biodegradation experiments, DOM from the two pasture streams was altered to a greater extent than DOM from the forest streams, with formulas with H/C and O/C ranges similar to protein (H/C = 1.5-2.2, O/C = 0.3-0.67), lipid (H/C = 1.5-2.0, O/C = 0-0.3), and unsaturated hydrocarbon (H/C = 0.7-1.5, O/C = 0-0.1) being the most bioreactive groups. Aromatic compound formulas including CAS were preferentially removed during combined light+bacterial incubations, supporting the contention that black carbon is labile to light alterations. Collectively, our data demonstrate that headwater DOM composition contains integrative information on watershed sources and processes, and the application of ESI-FTICR-MS technique offers additional insights into compound composition and reactivity unrevealed by fluorescence and stable carbon isotopic measurements.

Inter-annual variation of persistent organic pollutants (POPS) in an Antarctic top predator Arctocephalus gazella.

Persistent organic pollutants (POPs), contaminants that may bioaccumulate in upper trophic level organisms, were detected in the milk of a top predator, the Antarctic fur seal (Arctocephalus gazella). Multiparous females had significantly lower concentrations of certain POPs (trans-nonachlor, p,p'-DDE, and several PCBs) in their milk than primiparous females, likely due to the annual lactational transfer of the POP burden from mother to pup. Furthermore, there were significant interannual differences in POP concentrations in multiparous females' milk from five breeding seasons between 2000 and 2011. Decreasing trends in concentrations of certain POPs over the recent decade coincide with declining global emissions, yet atmospheric concentrations in the Antarctic are not always consistent with global trends, suggesting that additional factors may contribute to temporal trends of POPs in fur seals. Climate shifts and corresponding availability of krill over the past decade were not consistent with trends observed in POP concentrations in fur seal milk, suggesting that climate may not be a key factor. Additional mechanisms, such as variability in the geographic ranges of individual seals during overwintering migrations are discussed and should be explored further.

Effluent organic nitrogen (EON): bioavailability and photochemical and salinity-mediated release.

The goal of this study was to investigate three potential ways that the soluble organic nitrogen (N) fraction of wastewater treatment plant (WWTP) effluents, termed effluent organic N (EON), could contribute to coastal eutrophication--direct biological removal, photochemical release of labile compounds, and salinity-mediated release of ammonium (NH4+). Effluents from two WWTPs were used in the experiments. For the bioassays, EON was added to water from four salinities (approximately 0 to 30) collected from the James River (VA) in August 2008, and then concentrations of N and phosphorus compounds were measured periodically over 48 h. Bioassay results, based on changes in DON concentrations, indicate that some fraction of the EON was removed and that the degree of EON removal varied between effluents and with salinity. Further, we caution that bioassay results should be interpreted within a broad context of detailed information on chemical characterization. EON from both WWTPs was also photoreactive, with labile NH4+ and dissolved primary amines released during exposure to sunlight. We also present the first data that demonstrate that when EON is exposed to higher salinities, increasing amounts of NH4+ are released, further facilitating EON use as effluent transits from freshwater through estuaries to the coast.

Nutrient enrichment and food web composition affect ecosystem metabolism in an experimental seagrass habitat.

BACKGROUND: Food web composition and resource levels can influence ecosystem properties such as productivity and elemental cycles. In particular, herbivores occupy a central place in food webs as the species richness and composition of this trophic level may simultaneously influence the transmission of resource and predator effects to higher and lower trophic levels, respectively. Yet, these interactions are poorly understood. METHODOLOGY/PRINCIPAL FINDINGS: Using an experimental seagrass mesocosm system, we factorially manipulated water column nutrient concentrations, food chain length, and diversity of crustacean grazers to address two questions: (1) Does food web composition modulate the effects of nutrient enrichment on plant and grazer biomasses and stoichiometry? (2) Do ecosystem fluxes of dissolved oxygen and nutrients more closely reflect above-ground biomass and community structure or sediment processes? Nutrient enrichment and grazer presence generally had strong effects on biomass accumulation, stoichiometry, and ecosystem fluxes, whereas predator effects were weaker or absent. Nutrient enrichment had little effect on producer biomass or net ecosystem production but strongly increased seagrass nutrient content, ecosystem flux rates, and grazer secondary production, suggesting that enhanced production was efficiently transferred from producers to herbivores. Gross ecosystem production (oxygen evolution) correlated positively with above-ground plant biomass, whereas inorganic nutrient fluxes were unrelated to plant or grazer biomasses, suggesting dominance by sediment microbial processes. Finally, grazer richness significantly stabilized ecosystem processes, as predators decreased ecosystem production and respiration only in the zero- and one- species grazer treatments. CONCLUSIONS/SIGNIFICANCE: Overall, our results indicate that consumer presence and species composition strongly influence ecosystem responses to nutrient enrichment, and that increasing herbivore diversity can stabilize ecosystem flux rates in the face of perturbations.

Changes in sediment and organic carbon accumulation in a highly-disturbed ecosystem: the Sacramento-San Joaquin River Delta (California, USA).

We used the Sacramento-San Joaquin River Delta CA (Delta, hereafter) as a model system for understanding how human activities influence the delivery of sediment and total organic carbon (TOC) over the past 50-60 years. Sediment cores were collected from sites within the Delta representing the Sacramento River (SAC), the San Joaquin River (SJR), and Franks Tract (FT), a flooded agricultural tract. A variety of anthropogenic tracers including (137)Cs, total DDE (Sigma DDE) and brominated diphenyl ether (BDE) congeners were used to quantify sediment accumulation rates. This information was combined with total organic carbon (TOC) profiles to quantify rates of TOC accumulation. Across the three sites, sediment and TOC accumulation rates were four to eight-fold higher prior to 1972. Changes in sediment and TOC accumulation were coincident with completion of several large reservoirs and increased agriculture and urbanization in the Delta watershed. Radiocarbon content of TOC indicated that much of the carbon delivered to the Delta is "pre-aged" reflecting processing in the Delta watershed or during transport to the sites rather than an input of predominantly contemporary carbon (e.g., 900-1400 years BP in surface sediments and 2200 yrs BP and 3610 yrs BP at the base of the SJR and FT cores, respectively). Together, these data suggest that human activities have altered the amount and age of TOC accumulating in the Delta since the 1940s.