Prioritizing Non-Carbon Dioxide Removal Mitigation Strategies Could Reduce the Negative Impacts Associated with Large-Scale Reliance on Negative Emissions.

Carbon dioxide removal (CDR) is necessary for reaching net zero emissions, with studies showing potential deployment at multi-GtCO2 scale by 2050. However, excessive reliance on future CDR entails serious risks, including delayed emissions cuts, lock-in of fossil infrastructure, and threats to sustainability from increased resource competition. This study highlights an alternative pathway─prioritizing near-term non-CDR mitigation and minimizing CDR dependence. We impose a 1 GtCO2 limit on global novel CDR deployment by 2050, forcing aggressive early emissions reductions compared to 8-22 GtCO2 in higher CDR scenarios. Our results reveal that this low CDR pathway significantly decreases fossil fuel use, greenhouse gas (GHG) emissions, and air pollutants compared to higher CDR pathways. Driving rapid energy transitions eases pressures on land (including food cropland), water, and fertilizer resources required for energy and negative emissions. However, these sustainability gains come with higher mitigation costs from greater near-term low/zero-carbon technology deployment for decarbonization. Overall, this work provides strong evidence for maximizing non-CDR strategies such as renewables, electrification, carbon neutral/negative fuels, and efficiency now rather than betting on uncertain future CDR scaling. Ambitious near-term mitigation in this decade is essential to prevent lock-in and offer the best chance of successful deep decarbonization. Our constrained CDR scenario offers a robust pathway to achieving net zero emissions with limited sustainability impacts.

Deployment expectations of multi-gigatonne scale carbon removal could have adverse impacts on Asia's energy-water-land nexus.

Existing studies indicate that future global carbon dioxide (CO2) removal (CDR) efforts could largely be concentrated in Asia. However, there is limited understanding of how individual Asian countries and regions will respond to varying and uncertain scales of future CDR concerning their energy-land-water system. We address this gap by modeling various levels of CDR-reliant pathways under climate change ambitions in Asia. We find that high CDR reliance leads to residual fossil fuel and industry emissions of about 8 Gigatonnes CO2yr-1 (GtCO2yr-1) by 2050, compared to less than 1 GtCO2yr-1 under moderate-to-low CDR reliance. Moreover, expectations of multi-gigatonne CDR could delay the achievement of domestic net zero CO2 emissions for several Asian countries and regions, and lead to higher land allocation and fertilizer demand for bioenergy crop cultivation. Here, we show that Asian countries and regions should prioritize emission reduction strategies while capitalizing on the advantages of carbon removal when it is most viable.

Air-water fluxes of N2O and CH4 during microalgae (Staurosira sp.) cultivation in an open raceway pond.

The industrial-scale production of biofuels from cultivated microalgae has gained considerable interest in the last several decades. While the climate benefits of microalgae cultivation that result from the capture of atmospheric CO(2) are known, the counteracting effect from the potential emission of other greenhouse gases has not been well quantified. Here, we report the results of a study conducted at an industrial pilot facility in Hawaii to determine the air-water fluxes of N(2)O and CH(4) from open raceway ponds used to grow the marine diatom Staurosira sp. as a feedstock for biofuel. Dissolved O(2), CH(4), and N(2)O concentrations were measured over a 24 h cycle. During this time, four SF(6) tracer release experiments were conducted to quantify gas transfer velocities in the ponds, and these were then used to calculate air-water fluxes. Our results show that pond waters were consistently supersaturated with CH(4) (up to 725%) resulting in an average emission of 19.9 ± 5.6 µmol CH(4) m(-2) d(-1). Upon NO(3)(-) depletion, the pond shifted from being a source to being a sink of N(2)O, with an overall net uptake during the experimental period of 3.4 ± 3.5 µmol N(2)O m(-2) d(-1). The air-water fluxes of N(2)O and CH(4) expressed as CO(2) equivalents of global warming potential were 2 orders of magnitude smaller than the overall CO(2) uptake by the microalgae.

Computational prediction and experimental verification of new MAP kinase docking sites and substrates including Gli transcription factors.

In order to fully understand protein kinase networks, new methods are needed to identify regulators and substrates of kinases, especially for weakly expressed proteins. Here we have developed a hybrid computational search algorithm that combines machine learning and expert knowledge to identify kinase docking sites, and used this algorithm to search the human genome for novel MAP kinase substrates and regulators focused on the JNK family of MAP kinases. Predictions were tested by peptide array followed by rigorous biochemical verification with in vitro binding and kinase assays on wild-type and mutant proteins. Using this procedure, we found new 'D-site' class docking sites in previously known JNK substrates (hnRNP-K, PPM1J/PP2Czeta), as well as new JNK-interacting proteins (MLL4, NEIL1). Finally, we identified new D-site-dependent MAPK substrates, including the hedgehog-regulated transcription factors Gli1 and Gli3, suggesting that a direct connection between MAP kinase and hedgehog signaling may occur at the level of these key regulators. These results demonstrate that a genome-wide search for MAP kinase docking sites can be used to find new docking sites and substrates.

Influence of water management and natural variability on dissolved inorganic carbon dynamics in a mangrove-dominated estuary.

High-resolution time series measurements of temperature, salinity, pH and pCO2 were made during the period October 2014-September 2015 at the midpoint of Shark River, a 15km tidal river that originates in the freshwater Everglades of south Florida (USA) and discharges into the Gulf of Mexico. Dissolved inorganic carbon dynamics in this system vary over time, and during this study could be classified into three distinct regimes corresponding to October 2014-February 2015 (a wet to dry season transition period), March-May 2015 (dry period) and July-September 2015 (wet period). Average net longitudinal dissolved inorganic carbon (DIC) fluxes and air-water CO2 fluxes from the Shark River estuary were determined for the three periods. Net DIC fluxes to the coast were estimated to vary between 23.2 and 25.4×105mold-1 with an average daily DIC flux of 24.3×105mold-1 during the year of study. CO2 emissions ranged between 5.5 and 7.8×105mold-1 with an average daily value of 6.4×105mold-1 during the year. The differences in estuarine carbon fluxes during the study period are attributed to differences in the relative importance of hydro-climatological drivers. Results suggest that, during months characterized by reduced rainfall, carbon fluxes are affected by water management via control structures in the upstream Everglades marshes. During months with high rainfall, when culverts are closed and rainfall events are more frequent, carbon fluxes depend more on other forcings, such as rainfall and groundwater discharge.

Advances in quantifying air-sea gas exchange and environmental forcing.

The past decade has seen a substantial amount of research on air-sea gas exchange and its environmental controls. These studies have significantly advanced the understanding of processes that control gas transfer, led to higher quality field measurements, and improved estimates of the flux of climate-relevant gases between the ocean and atmosphere. This review discusses the fundamental principles of air-sea gas transfer and recent developments in gas transfer theory, parameterizations, and measurement techniques in the context of the exchange of carbon dioxide. However, much of this discussion is applicable to any sparingly soluble, non-reactive gas. We show how the use of global variables of environmental forcing that have recently become available and gas exchange relationships that incorporate the main forcing factors will lead to improved estimates of global and regional air-sea gas fluxes based on better fundamental physical, chemical, and biological foundations.

Interacting JNK-docking sites in MKK7 promote binding and activation of JNK mitogen-activated protein kinases.

D-sites are a class of MAPK-docking sites that have been found in many MAPK regulators and substrates. A single functional, high affinity D-site has been identified near the N terminus of each of the MAPK kinases (MKKs or MEKs) MEK1, MEK2, MKK3, MKK4, and MKK6. Here we demonstrated that MKK7 recognizes its target JNK by a novel mechanism involving a partially cooperative interaction of three low affinity D-sites in the N-terminal domain of MKK7. Mutations of the conserved residues within any one of the three docking sites (D1, D2, and D3) disrupted the ability of the N-terminal domain of MKK7beta to bind JNK1 by about 50-70%. Moreover, mutation of any two of the three D-sites reduced binding by about 80-90%, and mutation of all three reduced binding by 95%. Full-length MKK7 containing combined D1/D2 mutations was compromised for binding to JNK1 and exhibited reduced JNK1 kinase activity when compared with wild-type MKK7. Peptide versions of the D-sites from MKK4 or the JIP-1 scaffold protein inhibited MKK7-JNK binding, suggesting that all three JNK regulators bind to the same region of JNK. Moreover, peptide versions of any of the three D-sites of MKK7 inhibited the ability of JNK1 and JNK2 to phosphorylate their transcription factor substrates c-Jun and ATF2, suggesting that D-site-containing substrates also compete with MKK7 for docking to JNK. Finally, MKK7-derived D-site peptides exhibited selective inhibition of JNK1 versus ERK2. We conclude that MKK7 contains three JNK-docking sites that interact to selectively bind JNK and contribute to JNK signal transmission and specificity.

Seasonal variability and long term trends of chlorofluorocarbon mixing ratios in the unsaturated zone.

To investigate processes that might affect chlorofluorocarbon (CFC) mixing ratios at the water table, a time series was obtained of unsaturated zone soil gas CFCs to depths of ca. 4 m at a site near New York City (NYC). Observed CFC 11, 12, and 113 mixing ratios were lower in winter than expected from either a local, high-resolution time series or remote atmospheric mixing ratios. A diffusion model, which includes seasonal changes in soil temperature, moisture, and CFC solubility, reproduces to first order the observed soil gas mixing ratios for CFC 11 and 12. Underestimation by the model of the seasonal cycle of CFC 11 points to changing levels of sorption to soils due to seasonal changes in temperature as an additional cause of the cycle seen in CFC 11 mixing ratios in soil air. In the case of spring recharge, low CFC mixing ratios in soil air caused by increased solubility may result in low CFC 11 concentrations in groundwater and, when dating groundwater recharged before the 1990s with CFCs, older apparent ages by up to 4 years. Attempts to observe average atmospheric CFC levels from soil gas are also significantly hindered by these seasonal fluctuations. Our results indicate the importance of considering seasonal changes in soil temperature when making precise observations of even very moderately soluble gases in the unsaturated zone and shallow groundwater.

Distribution of atmospheric SF6 near a large urban area as recorded in the vadose zone.

Local emissions of SF6 are of interest for studying their impact on the use of SF6 as a groundwater-dating tool near source regions as well as for investigating the spatial distributions of (inert) gaseous compounds spreading from urban or industrial centers. A precondition for the use of SF6 in such studies is the capability to document the temporal and spatial evolution of SF6 in and around source regions with sufficient resolution. Here we present a time series of SF6 measurements in soil air at a site (Sparkill, NY) about 25 km north of New York City carried out between May 2000 and January 2002. The data show that, below about 2 m depth, the vadose zone integrates atmospheric SF6 mixing ratios over time scales greater than 1 month. SF6 mixing ratios in soil air at these depths match averaged high-resolution atmospheric measurements performed at Lamont-Doherty Earth Observatory in Palisades, NY, located about 3 km south of Sparkill. To a first-order approximation, a simple one-dimensional diffusion model reproduces the measured SF6 profiles in the vadose zone, suggesting that the soil indeed acts as a low-pass filter for inert atmospheric gases. These findings indicate that measurements of soil air can be used to determine the spatial pattern of SF6 excess relative to the remote atmosphere for a given region. A transect of soil profiles from Manhattan to the tip of Long Island indicates that emissions from sites close to New York City lead to significant SF6 excesses (ca. 25% or more) above the clean air mixing ratios over distances of the order of 80 km.

Determination of longitudinal dispersion coefficient and net advection in the tidal hudson river with a large-scale, high resolution SF6 tracer release experiment.

Physical processes such as advection, dispersion, and air-water gas exchange play important roles in determining the movement and change in concentration of contaminants discharged into rivers. In the following, we report results from a large-scale SF6 tracer release experiment conducted in the tidal Hudson Riverto examine longitudinal dispersion and net advection. SF6 was injected into the Hudson River near Newburgh, NY, and surveyed for 13 days using a new, fully automated, high-resolution SF6 sampling and analysis system. Net down river advection of the water body originally tagged with SF6 was slow, averaging mean displacement rates of about 0.5 +/- 0.2 km d(-1). In contrast, spreading of the tracer was driven by tidal movement, causing rapid mixing of the water up and down river. By examining the change in the second moment of the tracer distribution with time, we determined the mean longitudinal dispersion coefficient to be 70.1 +/- 4.3 m2 s(-1). Temporal evolution of the SF6 inventory indicates an average gas transfer velocity over the period of the experiment of 6.5 +/- 0.5 cm h(-1) (1.56 +/- 0.12 m d(-1)). Vertical profiles show that mixing into the bottom layers of the river, in places reaching more than 53 m, seemed to be rapid.

Transport dynamics in a sheltered estuary and connecting tidal straits: SF6 tracer study in New York Harbor.

In July 2002, approximately 0.9 mol of sulfur hexafluoride (SF6) was injected into Newark Bay, NJ, a 14 km2 estuary that forms part of New York Harbor, to investigate circulation, mixing, and the transport and fate of solutes. The SF6 tracer was observed over 11 consecutive days using a high-resolution measurement system. Total tracer mass in the sheltered waters declined quasiexponentially at a rate of 0.29 +/- 0.03 d(-1). Air-water gas exchange was estimated to account for 56% of tracer mass loss, upon the basis of wind speed/gas exchange parametrizations. Large-scale tidal transfer of solutes through the Kill van Kull strait (7 km long) caused net seaward flushing contrary to the apparent residual circulation. Seaward transport via the Arthur Kill strait (20 km long) appeared to depend on longitudinal dispersion, residual circulation, and freshwater discharge and was approximately 1 order of magnitude lower. The loss rate due to flushing alone was 0.13 +/- 0.02 d(-1), indicating a mean residence time for water and solutes in Newark Bay of approximately 8 days (without gas exchange). The experiment provides direct visualization of the transport of a released contaminant, and suggests a relationship between the length and configuration of tidal straits and related transport of solutes.

A docking site in MKK4 mediates high affinity binding to JNK MAPKs and competes with similar docking sites in JNK substrates.

Specific docking interactions between MAPKs and their activating MAPK kinases (MKKs or MEKs) are crucial for efficient and accurate signal transmission. Here, we report the identification of a MAPK-docking site, or "D-site," in the N terminus of human MKK4/JNKK1. This docking site conforms to the consensus sequence for known D-sites in other MKKs and contains the first of the two cleavage sites for anthrax lethal factor protease that have been found in the N terminus of MKK4. This docking site was both necessary and sufficient for the high affinity binding of the MAPKs JNK1, JNK2, JNK3, p38 alpha, and p38 beta to MKK4. Mutations that altered conserved residues in this docking site reduced JNK/p38 binding. In addition, a peptide version of this docking site, as well as a peptide version of the JNK-binding site of the JIP-1 scaffold protein, inhibited both MKK4/JNK binding and MKK4-mediated phosphorylation of JNK1. These same peptides also inhibited JNK2-mediated phosphorylation of c-Jun and ATF2, suggesting that transcription factors, MKK4, and the JIP scaffold compete for docking to JNK. Finally, the selectivity of the MKK4, MEK1, and MEK2 D-sites for JNK versus ERK was quantified. The MEK1 and MEK2 D-sites displayed a strong selectivity for their cognate MAPK (ERK2) versus a non-cognate MAPK (JNK). In contrast, the MKK4 D-site exhibited only limited selectivity for JNK versus ERK.

Effect of tides on solute flushing from a strait: imaging flow and transport in the East River with SF6.

In June 2003, two injections of approximately 3.9 mol of sulfur hexafluoride (SF6) were made 8 days apart in the East River, a 25 km tidal strait, to observe solute mixing and dissipation. The first injection occurred at slack before flood, and the second at slack before ebb (flood = northward flow). Tidally synchronized surveys of the SF6 tracer patch, supplemented by vertical profiles, were conducted by boat for 6 and 4 days following the flood and ebb injections, respectively. Residence times for the tracer-tagged water mass in the East River were estimated to be 3.3 +/- 0.7 days and 1.7 +/- 0.5 days for the flood and ebb injections, respectively, after correcting SF6 inventories for losses of SF6 from the water column by air-water gas exchange. The data indicate that the majority of East River solutes are transported to New York Harbor and that tidal mixing dominates subtidal circulation with respectto solute transport. Surveys of the adjacent lower Hudson River revealed a northward-moving, intermediate layer of East River water. Our results suggest that tidal phasing of contaminant discharges in the East River could reduce environmental impacts, by increasing flushing rates and directing a greater fraction of material away from Long Island Sound.