Geochemical properties of blue carbon sediments through an elevation gradient: study of an anthropogenically impacted coastal lagoon.

Global research is showing that coastal blue carbon ecosystems are vulnerable to climate change driven threats including accelerated sea-level rise and prolonged periods of drought. Furthermore, direct anthropogenic impacts present immediate threats through deterioration of coastal water quality, land reclamation, long-term impact to sediment biogeochemical cycling. These threats will invariably alter the future efficacy of carbon (C) sequestration processes and it is imperative that currently existing blue carbon habitats be protected. Knowledge of underlying biogeochemical, physical and hydrological interactions occurring in functioning blue carbon habitats is essential for developing strategies to mitigate threats, and promote conditions to optimise C sequestration/storage. In this current work, we investigated how sediment geochemistry (0-10 cm depth) responds to elevation, an edaphic factor driven by long-term hydrological regimes consequently exerting control over particle sedimentation rates and vegetation succession. This study was performed in an anthropogenically impacted blue carbon habitat along a coastal ecotone encompassing an elevation gradient transect from intertidal sediments (un-vegetated and covered daily by tidal water), through vegetated salt marsh sediments (periodically covered by spring tides and flooding events), on Bull Island, Dublin Bay. We determined the quantity and distributions of bulk geochemical characteristics in sediments through the elevation gradient, including total organic carbon (TOC), total nitrogen (TN), total metals, silt, clay, and also, 16 individual polyaromatic hydrocarbon's (PAH's) as an indication of anthropogenic input. Elevation measurements for sample sites were determined on this gradient using a LiDAR scanner accompanied by an IGI inertial measurement unit (IMU) on board a light aircraft. Considering the gradient from the Tidal mud zone (T), through the low-mid marsh (M) to the most elevated upper marsh (H), there were significant differences between all zones for many measured environmental variables. The results of significance testing using Kruskal-Wallis analysis revealed, that %C, %N, PAH (µg/g), Mn (mg/kg), TOC:NH4 + and pH are significantly different between all zones on the elevation gradient. The highest values for all these variables exists (excluding pH which followed a reverse trend) in zone H, decreasing in zone M and lowest in the un-vegetated zone T. TC content is 16 fold higher overall in vegetated (3.43 -21.84%) than uninhabited (0.21-0.56%) sediments. TN was over 50 times higher (0.24-1.76%), more specifically increasing in % mass on approach to the upper salt marsh with distance from the tidal flats sediments zone T (0.002-0.05%). Clay and silt distributions were greatest in vegetated sediments, increasing in % content towards upper marsh zones The retention of water, metals, PAHs, mud, chloride ions, NH4 +, PO4 3- and SO4 2- increased with elevated C concentrations, concurrently where pH significantly decreased. Sediments were categorized with respect to PAH contamination where all SM samples were placed in the high polluted category. The results highlight the ability of Blue C sediments to immobilise increasing levels of C, N, and metals, and PAH with over time and with both lateral and vertical expansion. This study provides a valuable data set for an anthropogenically impacted blue carbon habitat predicted to suffer from sea-level rise and exponential urban development. Graphical abstract: Summarized results from this study demonstrating the geochemical changes through an elevation gradient, with a transect encompassing intertidal sediments through supratidal salt marsh sediments within Bull Island's blue carbon lagoon zones. Supplementary Information: The online version contains supplementary material available at 10.1007/s10533-022-00974-0.

Biogeochemical properties of blue carbon sediments influence the distribution and monomer composition of bacterial polyhydroxyalkanoates (PHA).

Coastal wetlands are highly efficient 'blue carbon' sinks which contribute to mitigating climate change through the long-term removal of atmospheric CO2 and capture of carbon (C). Microorganisms are integral to C sequestration in blue carbon sediments and face a myriad of natural and anthropogenic pressures yet their adaptive responses are poorly understood. One such response in bacteria is the alteration of biomass lipids, specifically through the accumulation of polyhydroxyalkanoates (PHAs) and alteration of membrane phospholipid fatty acids (PLFA). PHAs are highly reduced bacterial storage polymers that increase bacterial fitness in changing environments. In this study, we investigated the distribution of microbial PHA, PLFA profiles, community structure and response to changes in sediment geochemistry along an elevation gradient from intertidal to vegetated supratidal sediments. We found highest PHA accumulation, monomer diversity and expression of lipid stress indices in elevated and vegetated sediments where C, nitrogen (N), PAH and heavy metals increased, and pH was significantly lower. This was accompanied by a reduction in bacterial diversity and a shift to higher abundances of microbial community members favouring complex C degradation. Results presented here describe a connection between bacterial PHA accumulation, membrane lipid adaptation, microbial community composition and polluted C rich sediments. Graphical Abstract: Geochemical, microbiological and polyhydroxyalkanoate (PHA) gradient in a blue carbon zone. Supplementary Information: The online version contains supplementary material available at 10.1007/s10533-022-01008-5.

Two-Dimensional Electronic Spectroscopy Reveals Vibrational Modes Coupled to Charge Transfer in a Julolidine-BODIPY Dyad.

Understanding charge transfer (CT) dynamics in molecular donor-acceptor (D-A) dyads can provide insight into developing efficient D-A molecules for capturing solar energy. Here, we characterize the excited-state evolution of a julolidine-BODIPY (Jul-BD) D-A system with an emissive CT state using time-resolved fluorescence, femtosecond transient absorption, and two-dimensional electronic spectroscopies. Comparison of these results with those from phenyl-BODIPY (Ph-BD) allows us to identify the dynamics at play during CT state formation and its subsequent conversion to either a fully charge-separated or triplet state. Photoexcitation of Jul-BD in tetrahydrofuran results in the formation of an initial emissive CT state that relaxes before fully charge-separating. In contrast, Jul-BD in toluene exhibits similar CT state dynamics, albeit at slower timescales, before decaying to a terminal triplet species. Quantum beat analysis at early times in both solvents shows several vibronic modes, which are corroborated using density functional theory (DFT) calculations. For Ph-BD, a single 220 cm-1 compression mode about the single bond linking the phenyl to BODIPY modulates their orbital overlap. Three active vibronic modes, 147, 174, and 214 cm-1, are found in Jul-BD, regardless of the dielectric constant of the medium. These motions correspond to compression and torsional motions along the single bond joining Jul to BD and are responsible for the evolution of the spontaneous and stimulated emission features in the time-resolved spectroscopic data, which is further supported by time-dependent DFT calculations of the steady-state absorption spectrum of the Jul-BD as a function of increasing D-A dihedral core angle. These findings show how torsional and compression motions can play a pivotal role in intramolecular CT between a D and an A linked by a single bond.

Direct Observation of Modulated Radical Spin States in Metal-Organic Frameworks by Controlled Flexibility.

Owing to their switchable spin states and dynamic electronic character, organic-based radical species have been invoked in phenomena unique to a variety of fields. When incorporated in solid state materials, generation of organic radicals proves challenging due to aggregation. Metal-organic frameworks (MOFs) are promising candidates for immobilization and stabilization of organic radicals because of the tunable spatial arrangement of organic linkers and metal nodes, which sequesters the reactive species. Herein, a flexible, redox-active tetracarboxylic acid linker bearing two imidazole units was chosen to construct a new Zr6-MOF, NU-910, with scu topology. By exploiting the structural flexibility of NU-910, we successfully modulate the dynamics between an isolated organic radical species and an organic radical π-dimer species in the MOF system. Single-crystal X-ray diffraction analysis reveals that through solvent exchange from N,N-diethylformamide to acetone, NU-910 undergoes a structural contraction with interlinker distances decreasing from 8.32 Å to 3.20 Å at 100 K. Organic radical species on the bridging linkers are generated via UV light irradiation. Direct observation of temperature-induced spin switches from an isolated radical species to a magnetically silent radical π-dimer in NU-910 after irradiation in the solid state was achieved via variable-temperature single-crystal X-ray diffraction and variable-temperature electron paramagnetic resonance spectroscopy. Ultraviolet-visible-near infrared spectroscopy and density functional theory calculations further substantiated the formation of a radical cation π-dimer upon irradiation. This work demonstrates the potential of using flexible MOFs as a platform to modulate radical spin states in the solid phase.

Exploring Photogenerated Molecular Quartet States as Spin Qubits and Qudits.

Photogenerated molecular spin systems hold great promise for applications in quantum information science because they can be prepared in well-defined spin states at modest temperatures, they often exhibit long coherence times, and their properties can be tuned by chemical synthesis. Here, we investigate a molecular spin system composed of a 1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) chromophore covalently linked to a stable nitroxide radical (TEMPO) by optical and electron paramagnetic resonance (EPR) techniques. Upon photoexcitation of the spin system, a quartet state is formed as confirmed by transient nutation experiments. This quartet state has spin polarization lifetimes longer than 0.1 ms and is characterized by relatively long coherence times of ∼1.8 µs even at 80 K. Rabi oscillation experiments reveal that more than 60 single-qubit logic operations can be performed with this system at 80 K. The large magnitude of the nitroxide 14N hyperfine coupling in the quartet state of PDI-TEMPO is resolved in the transient EPR spectra and leads to a further splitting of the quartet state electron spin sublevels. We discuss the properties of this photogenerated multilevel system, comprising 12 electron-nuclear spin states, in the context of its viability as a qubit for applications in quantum information science.

Interaction of Photogenerated Spin Qubit Pairs with a Third Electron Spin in DNA Hairpins.

The designing of tunable molecular systems that can host spin qubits is a promising strategy for advancing the development of quantum information science (QIS) applications. Photogenerated radical pairs are good spin qubit pair (SQP) candidates because they can be initialized in a pure quantum state that exhibits relatively long coherence times. DNA is a well-studied molecular system that allows for control of energetics and spatial specificity through careful design and thus serves as a tunable scaffold on which to control multispin interactions. Here, we examine a series of DNA hairpins that use naphthalenediimide (NDI) as the hairpin linker. Photoexcitation of the NDI leads to subnanosecond oxidation of guanine (G) within the duplex or a stilbenediether (Sd) end-cap to give NDI•--G•+ or NDI•--Sd•+ SQPs, respectively. A 2,2,6,6-tetramethylpiperdinyl-1-oxyl (TEMPO) stable radical is covalently attached to the hairpin at varying distances from the SQP spins. While TEMPO has a minimal effect on the SQP formation and decay dynamics, EPR spectroscopy indicates that there are significant spin-spin dipolar interactions between the SQP and TEMPO. We also demonstrate the ability to implement more complex spin manipulations of the NDI•--Sd•+-TEMPO system using pulse-EPR techniques, which is important for developing DNA hairpins for QIS applications.

Excitation Energy Transfer and Exchange-Mediated Quartet State Formation in Porphyrin-Trityl Systems.

Photogenerated multi-spin systems hold great promise for a range of technological applications in various fields, including molecular spintronics and artificial photosynthesis. However, the further development of these applications, via targeted design of materials with specific magnetic properties, currently still suffers from a lack of understanding of the factors influencing the underlying excited state dynamics and mechanisms on a molecular level. In particular, systematic studies, making use of different techniques to obtain complementary information, are largely missing. This work investigates the photophysics and magnetic properties of a series of three covalently-linked porphyrin-trityl compounds, bridged by a phenyl spacer. By combining the results from femtosecond transient absorption and electron paramagnetic resonance spectroscopies, we determine the efficiencies of the competing excited state reaction pathways and characterise the magnetic properties of the individual spin states, formed by the interaction between the chromophore triplet and the stable radical. The differences observed for the three investigated compounds are rationalised in the context of available theoretical models and the implications of the results of this study for the design of a molecular system with an improved intersystem crossing efficiency are discussed.

Metalated Porphyrin Stable Free Radicals: Exploration of Electron Spin Communication and Dynamics.

Switchable coupling between two qubits is important for quantum information science (QIS). As a proof of concept, a series of mesosubstituted porphyrins have been synthesized with a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl stable free radical (SFR) appended and metalated with Cu(II), Ni(II), and Zn(II) in order to explore the interaction between the SFR doublet state and metalloporphyrin. The spin state of the porphyrin varies upon metal insertion, where Zn(II) is a diamagnetic metal, Cu(II) is paramagnetic, and Ni(II) can be switched from a diamagnetic square-planar structure to a paramagnetic octahedral state by complexation with a solvent (i.e., pyridine or tetrahydrofuran). Time-resolved electron paramagnetic resonance (EPR) measurements reveal that upon photoexcitation, the Zn(II) and free-base porphyrin species demonstrate different magnetic exchange regimes between the porphyrin triplet excited states and the SFR doublet state, with the Zn derivative populating a quartet state (i.e., moderate magnetic exchange), whereas the free-base derivative remains a triplet (i.e., weak magnetic exchange). Transient absorption measurements corroborate the TREPR results, demonstrating a 66% increase in the singlet excited-state decay rate due to enhanced intersystem crossing for the Zn(II) derivative in comparison to a modest 14% enhancement for the free-base porphyrin. These results enable the realization of a switchable qubit coupler, depending upon Zn metal insertion to the free-base porphyrin, which has potential QIS applications.

Selectively Addressable Photogenerated Spin Qubit Pairs in DNA Hairpins.

Photoinduced electron transfer can produce radical pairs having two quantum entangled electron spins that can act as spin qubits in quantum information applications. Manipulation of these spin qubits requires selective addressing of each spin using microwave pulses. In this work, photogenerated spin qubit pairs are prepared within chromophore-modified DNA hairpins with varying spin qubit distances, and are probed using transient EPR spectroscopy. By performing pulse-EPR measurements on the shortest hairpin, selective addressing of each spin qubit comprising the pair is demonstrated. Furthermore, these spin qubit pairs have coherence times of more than 4 µs, which provides a comfortable time window for performing complex spin manipulations for quantum information applications. The applicability of these DNA-based photogenerated two-qubit systems is discussed in the context of quantum gate operations, specifically the controlled-NOT gate.