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The frequency and persistence of tidal inundation varies along the coastal terrestrial-aquatic interface, from frequently inundated wetlands to rarely inundated upland forests. This inundation gradient controls soil and sediment biogeochemistry and influence the exchange of soils and sediments from terrestrial to aquatic domains. Although a rich literature exist on studies of the influence of tidal waters on the biogeochemistry of coastal ecosystem soils, few studies have experimentally addressed the reverse question: How do soils (or sediments) from different coastal ecosystems influence the biogeochemistry of the tidal waters that inundate them? To better understand initial responses of coastal waters that flood coastal wetlands and uplands, we conducted short-term laboratory experiments where seawater was amended with sediments and soils collected across regional gradients of inundation exposure (i.e., frequently to rarely inundated) for 14 sites across the Mid-Atlantic, USA. Measured changes in dissolved oxygen and greenhouse gas concentrations were used to calculate gas consumption or production rates occurring during seawater exposure to terrestrial materials. We also measured soil and water physical and chemical properties to explore potential drivers. We observed higher oxygen consumption rates for seawater incubated with soils/sediments from frequently inundated locations and higher carbon dioxide production for seawater incubated with soils from rarely inundated transect locations. Incubations with soil from rarely inundated sites produced the highest global warming potential, primarily driven by carbon dioxide and secondarily by nitrous oxide. We also found environmental drivers of gas rates varied notably between transect locations. Our findings indicate that seawater responses to soil and sediment inputs across coastal terrestrial-aquatic interfaces exhibit some consistent patterns and high intra- and inter-site variability, suggesting potential biogeochemical feedback loops as inundation regimes shift inland. 

Abstract The Tocantins River contributes ∼5% of the total flux of water to the Amazon River plume in the Atlantic Ocean. Here, we evaluate monthly variability in the composition and abundance of carbon, nitrogen, and suspended sediment in the lower reaches of the Tocantins River from 2014 to 2016. Dissolved organic carbon concentrations generally increased during periods of high discharge and are ∼1.5 times lower than average concentrations at the mouth of the Amazon River. Dissolved inorganic carbon similarly increased during periods of high discharge. Total dissolved nitrogen and individual nitrogen species followed a similar temporal pattern, increasing during high water.predominated the dissolved inorganic nitrogen pool, followed by, and, characteristic of environments with a relatively low anthropogenic impact. Dissolved fractions represented 92% of the total carbon exported and 78% of the total nitrogen exported. The suspended particulate sediment flux was 2.72 × 10⁶ t yr⁻¹, with fine suspended sediment dominating (71.3%). Concentrations of carbon relative to nitrogen indicate a primarily terrigenous source of organic matter and CO₂derived from in situ respiration of this material during the rainy season and a primarily algal/bacterial source of organic matter during the dry season. Considering past estimates of dissolved carbon and nitrogen fluxes from the Amazon River to the Atlantic Ocean, the Tocantins River contributes 3% and 3.7% to total fluxes to the Amazon River plume region, respectively. While this contribution is relatively small, it may be influenced by future changes to the basin's land use and hydrology. 

Protic ruthenium complexes using the dihydroxybipyridine (dhbp) ligand combined with a spectator ligand (N,N = bpy, phen, dop, Bphen) have been studied for their potential activity vs. cancer cells and their photophysical luminescent properties. These complexes vary in the extent of π expansion and the use of proximal (6,6′-dhbp) or distal (4,4′-dhbp) hydroxy groups. Eight complexes are studied herein as the acidic (OH bearing) form, [(N,N)2Ru(n,n′-dhbp)]Cl2, or as the doubly deprotonated (O− bearing) form. Thus, the presence of these two protonation states gives 16 complexes that have been isolated and studied. Complex 7A, [(dop)2Ru(4,4′-dhbp)]Cl2, has been recently synthesized and characterized spectroscopically and by X-ray crystallography. The deprotonated forms of three complexes are also reported herein for the first time. The other complexes studied have been synthesized previously. Three complexes are light-activated and exhibit photocytotoxicity. The log(Do/w) values of the complexes are used herein to correlate photocytotoxicity with improved cellular uptake. For Ru complexes 1–4 bearing the 6,6′-dhbp ligand, photoluminescence studies (all in deaerated acetonitrile) have revealed that steric strain leads to photodissociation which tends to reduce photoluminescent lifetimes and quantum yields in both protonation states. For Ru complexes 5–8 bearing the 4,4′-dhbp ligand, the deprotonated Ru complexes (5B–8B) have low photoluminescent lifetimes and quantum yields due to quenching that is proposed to involve the 3LLCT excited state and charge transfer from the [O2-bpy]2− ligand to the N,N spectator ligand. The protonated OH bearing 4,4′-dhbp Ru complexes (5A–8A) have long luminescence lifetimes which increase with increasing π expansion on the N,N spectator ligand. The Bphen complex, 8A, has the longest lifetime of the series at 3.45 μs and a photoluminescence quantum yield of 18.7%. This Ru complex also exhibits the best photocytotoxicity of the series. A long luminescence lifetime is correlated with greater singlet oxygen quantum yields because the triplet excited state is presumably long-lived enough to interact with 3O2 to yield 1O2. 

Optical water types (OWTs) were identified from an in situ dataset of concomitant biogeochemical and optical parameters acquired in the Amazon River and its tributaries, in the Lower Amazon region, at different hydrological conditions from 2014 to 2017. A seasonal bio-optical characterization was performed. The k-means classification was applied to the in situ normalized reflectance spectra (rn(λ)), allowing the identification of four OWTs. An optical index method was also applied to the rn(λ) defining the thresholds of the OWTs. Next, level-3 Sentinel-3 Ocean and Land Color Instrument images representative of the seasonal discharge conditions were classified using the identified in situ OWTs as reference. The differences between Amazon River and clearwater tributary OWTs were dependent on the hydrological dynamics of the Amazon River, also showing a strong seasonal variability. Each OWT was associated with a specific bio-optical and biogeochemical environment assessed from the corresponding absorption coefficient values of colored dissolved organic matter (aCDOM) and particulate matter (ap), chlorophyll-a and suspended particulate matter (SPM) concentrations, and aCDOM/ap ratio. The rising water season presented a unique OWT with high SPM concentration and high relative contribution of ap to total absorption compared to the other OWTs. This bio-optical characterization of Lower Amazon River waters represents a first step for developing remote sensing inversion models adjusted to the optical complexity of this region.