Surface Nitrate Research Articles

Evaluating the influence of environmental variables on the length-weight relationship and prediction modelling in flathead grey mullet, Mugil cephalus Linnaeus, 1758.

Fish stocks that are grown under diverse environmental conditions have different biometric relationships and growth patterns. The biometric length-weight relationship (LWR) is an essential fishery assessment tool, as fish growth is continuous and depends on genetic and environmental factors. The present study attempts to understand the LWR of the flathead grey mullet, Mugil cephalus Linnaeus, 1758, from different locations. The study area encompassed its distribution in the wild across freshwater location (one), coastal habitats (eight locations), and estuaries (six locations) in India to determine the relationship between various environmental parameters. Specimens (n = 476) of M. cephalus were collected from commercial catches and the length and weight of individual specimens were recorded. Monthly data from the study locations were extracted for nine environmental variables from the datasets downloaded from the Physical Oceanography Distributed Active Archive Center (PO.DAAC) and the Copernicus Marine Environment Monitoring Service (CMEMS) over 16 years (2002 to 2017) on the Geographical Information System platform. The parameters of the LWR, intercept 'a' and slope or regression coefficient 'b', varied from 0.005321 to 0.22182 and 2.235 to 3.173, respectively. The condition factor ranged from 0.92 to 1.41. The partial least squares (PLS) score scatter plot matrix indicated differences in the environmental variables between the locations. PLS analysis of the regression coefficient and environment parameters revealed that certain environment variables viz., sea surface temperature, salinity, dissolved oxygen, nitrate, and phosphate, played a positive role. However, chlorophyll, pH, silicate, and iron played a negative role in influencing weight growth across various locations. The results revealed that the M. cephalus specimens from three locations, Mandapam, Karwar, and Ratnagiri, possessed significantly higher fitness to their environment than those from the other six locations. The PLS model can be used to predict weight growth under the various environmental conditions of different ecosystems. The three identified locations are useful sites for the mariculture of this species considering their growth performance, the environmental variables, and their interactions. The results of this study will improve the management and conservation of exploited stocks in regions affected by climate change. Our results will also aid in making environment clearance decisions for coastal development projects and will improve the efficiency of mariculture systems.

Synergistic promotion effects of surface hydroxyl groups (-OH) and nitrate groups (-NO3) on catalytic ozonation of toluene over MnFe catalyst

A series of MnFe catalysts were prepared by hydrothermal synthesis combined with heat treatment at different temperatures. The characterizations demonstrated that MnFe-120 with both surface -OH and -NO3, MnFe-175 with surface -OH, MnFe-300 containing neither surface -OH nor -NO3, and MnFe-300-NO3 containing surface -NO3 were gained by drying or calcination and impregnation. The activity evaluation showed that the order of catalytic activity was MnFe-120 > MnFe-175 > MnFe-300-NO3 > MnFe-300. Further, characterizations and experiment results revealed that O3 adsorbed on the surface of the catalyst can interact with surface -OH and generated hydroxyl radicals (·OH). The presence of surface -NO3 provided more Lewis acid sites, thereby promoting H2O adsorption and conversion to the surface -OH, which supplemented the surface -OH consumed by the interaction with O3. It was deduced that the coexistence of surface -OH and -NO3 improved the production of·OH, which synergistically promoted the catalytic ozonation of toluene.

Modeling Nitrogen Balance for Pre-Assessment of Surface and Groundwater Nitrate (NO3-−N) Contamination from N–Fertilizer Application Loss: a Case of the Bilate Downstream Watershed Cropland

Modeling Nitrogen Balance for Pre-Assessment of Surface and Groundwater Nitrate (NO3-−N) Contamination from N–Fertilizer Application Loss: a Case of the Bilate Downstream Watershed Cropland

Increased night-time oxidation over China despite widespread decrease across the globe

Nitrogen oxides (NOx = NO + NO2) emitted from combustion and natural sources are reactive gases that regulate the composition of Earth’s atmosphere. Nocturnal oxidation driven by nitrate radicals is an important but poorly understood process in atmospheric chemistry, affecting the lifetimes of NOx and ozone and particulate pollution levels. Understanding the trends of nitrate radicals is important to formulating effective pollution mitigation strategies and understanding the influence of NOx on climate. Here we analyse publicly available monitoring data on NOx and ozone to assess production rates and trends of surface nitrate radicals from 2014 to 2021 across the globe. We show that nitrate radicals have undergone strong increases in China during 2014–2019 but exhibited modest decreases in the United States and the European Union. Accelerated night-time oxidation has shortened the lifetime of summer NOx in China by 30% during 2014–2019. This change will strongly affect ozone formation and has policy implications for the joint control of ozone and fine particulate pollution. Measurements show that night-time production of atmospheric nitrate radicals increased in China but decreased in the European Union and the United States from 2014 to 2019. This suggests the increasing contribution of night-time atmospheric oxidation in China to air pollution.

Nutrients and hydrography explain the composition of recent Mediterranean planktonic foraminiferal assemblages

The composition of planktonic foraminiferal assemblages in surface sediments of the Mediterranean Sea shows a pronounced zonal gradient. This gradient is different from what is observed in the open ocean, indicating that the assemblage composition may respond to environmental variables other than the otherwise dominant surface water temperature. Here we make use of a dataset of census counts of 18 taxonomic categories in 124 surface-sediment samples extracted from the ForCenS database to understand the main environmental factors affecting the composition of recent Mediterranean planktonic foraminiferal assemblages. The tested explanatory variables include temperature, salinity, chlorophyll, nitrate and phosphate concentrations in the surface waters, temperature, nitrate and phosphate concentrations at depth and thermal, salinity and density vertical gradients. The composition of the assemblages is aligned along two environmental gradients and redundancy analysis reveals that the tested variables explain a large portion (>70%) of the variance in the compositional data. The first environmental gradient reflects the nutrient content in the deep waters, affecting nutrient availability in the productive zone, while the second gradient is driven by higher (northern area) and lower (southern area) upward nutrient advection due to differences in density stratification, conditioned by the regional hydrography. Although sea surface temperature is the most reconstructed environmental variable from fossil assemblages of planktonic foraminifera, it seems to play a secondary role in the Mediterranean Sea. This, has implications for reconstructions of past oceanographic conditions in this region, opening up the possibility to reconstruct productivity instead, or next to, temperature.

Experimental and kinetic model evaluation of HONO production from surface nitrate photolysis

Solar irradiation plays a key role in promoting nitrous acid (HONO) production from surface enhanced photochemical reactions such as photolysis of nitrate. Nitrate anions are ubiquitous in ambient particles and on various outdoor and indoor surfaces, with reported surface density from 10−7 to 10−3 mol m−2. In this work, we measured HONO and NO2 production from surface nitrate photolysis under eight narrow bandwidth light sources with peak emission wavelengths ranging from 300 to 605 nm. We defined the probability of HONO and NO2 release per surface nitrate absorbing unit photon density of particular wavelength as “reactive cross section” of surface nitrate. Relative to the absorption cross section of gaseous HNO3, the reactive cross section of surface nitrate was found enhanced by up to 970-fold. The reactive cross section determined in our laboratory decreased from (6.3 ± 0.5) × 10−20 cm2 molecule−1 at 300 nm to (1.0 ± 0.3) × 10−24 cm2 molecule−1 at 605 nm, and showed a nonlinear relationship with the surface density of nitrate. Outdoor HONO production was mostly attributed to solar UV irradiation as expected, while underappreciated indoor HONO accumulation was also feasible considering HONO production induced by visible light and large specific surface area indoors. We then constructed a dynamic model to further evaluate the indoor HONO source in typical indoor environments. Photochemical properties of this HONO source lead to diurnal profiles in indoor HONO accumulation, with daily average HONO accumulation ranging from 1.1 to 17.8 ppb under various conditions. The model calculation confirmed that visible light substantially promotes surface nitrate photolysis and indoor HONO accumulation, with an average daily strength that is 0.28–0.34 mg h−1 at surface nitrate of 10−4 mol m−2 under simulated sunlight illumination. Our results call for direct measurements of indoor HONO in a variety of real indoor environments.

Wheat Straw Burial Enhances the Root Physiology, Productivity, and Water Utilization Efficiency of Rice under Alternative Wetting and Drying Irrigation

This study evaluated whether the straw burial and alternative wetting and drying (AWD) irrigation could improve the root activity, yield, and water utilization efficiency (WUE) of rice. Accordingly, we conducted a field experiment with three straw burial levels, i.e., with no straw burial (NSB), low straw burial 300 kg.ha−1 (LSB), and dense straw burial 800 kg.ha−1 (DSB), and three irrigation regimes, i.e., alternate wetting/moderate drying (AWMD), alternate wetting/severe drying (AWSD), and alternate wetting/critical drying (AWCD). Results showed that straw burial improved the root activity, rice yield, and WUE under AWD regimes. The combination AWMD×DSB resulted in the greatest values of total dry mass (1764.7 g/m2) and water use (853.1 mm). Conversely, the treatment AWCD × NSB led to the lowest values of total biomass (583.3 g/m2) and water use (321.8 mm). Root dry weight density (1.11 g cm−3) and root active absorption area (31.6 m2 plant−1) were higher in the treatment AWMD × DSB than root dry weight density (0.41 g cm−3) and root active absorption area (21.2 m2 plant−1) were in the treatment AWCD×NSB. The former combined treatment increased root oxidation ability (55.5 mg g−1 FWh−1), the root surface phosphatase activity (1.67 mg g−1 FWh−1) and nitrate reductase activity of root (14.4 μg g−1 h−1) while the latter considerably reduced the values of root oxidation ability (21.4 mg g−1 FWh−1), the root surface phosphatase activity (0.87 mg g−1 FWh−1) and nitrate reductase activity of root (5.8 μg g−1 h−1). The following conclusions can be drawn with regard to water use and biomass yield. (i) The reduction in water consumption was greater than the reduction in yield in the case of AWSD. (ii) The decline in water consumption was less than the decline in biomass yield in the case of AWCD. (iii) The increase in in water consumption was greater than the increase in biomass yield in the case of AWMD. Therefore, the indicators of WUE were recorded in the following order: AWSD > AWMD > AWCD. This study recommends AWD irrigation to improve the root growth traits that contribute to the greater biomass yield of rice. It also suggests that farmers should implement AWD irrigation after leaving wheat straw residues in the field, and followed by deep tillage, to mitigate the negative effect of drought stress caused by AWD irrigation, preserving plant growth without large biomass losses, and thus, addressing the constrains of straw residues and sustaining rice production under limited freshwater resources.

Mechanistic assessment of NO oxidative activation on tungsten-promoted ceria catalysts and its consequence for low-temperature NH3-SCR

Ceria has absorbed extensive interests in functioning as catalysts for low-temperature (LT) selective catalytic reduction (SCR) of NOx due to its abundant surface oxygen species and salient redox property. The mechanistic interpretations of how such redox property contributes to its LT-SCR activity, however, still remain debated. Here, we use a model tungsten-promoted ceria catalyst (WO3/CeO2), known as preeminent in LT-SCR reactions, and combine steady-state kinetic, structural characteristic and in situ spectroscopic experiments with theoretical treatments to reveal the mechanistic connections between NO oxidative activation and LT-SCR turnovers. We show that, compared with NO oxidation to NO2, NO oxidative activation to nitrite intermediates is both kinetically and thermodynamically more favorable; surface nitrate species are not detected in the present case, indicating their more difficult formation than nitrites. All these results thus suggest the prevalence of NO activation to nitrites over NO to nitrates or oxidation to NO2 and subsequent occurrence of fast SCR in the WO3/CeO2-catalyzed LT-SCR reaction. These findings progress the understanding of LT-SCR reaction mechanism on CeO2-based catalysts and convey a detailed perspective of different reaction intermediates and their consequences for LT-SCR turnovers, which may contribute to the rational design of catalysts towards further improved LT-SCR activity.

Remote Sensing of the Seasonal and Interannual Variability of Surface Chlorophyll-a Concentration in the Northwest Pacific over the Past 23 Years (1997–2020)

Phytoplankton in the northwest Pacific plays an important role in absorbing atmospheric CO2 and promoting the ocean carbon cycle. However, our knowledge on the long-term interannual variabilities of the phytoplankton biomass in this region is quite limited. In this study, based on the Chlorophyll-a concentration (Chl-a) time series observed from ocean color satellites of Sea-viewing Wide Field-of-view Sensor (SeaWiFS) and Moderate Resolution Imaging Spectroradiometer (MODIS) in the period of 1997–2020, we investigated the variabilities of Chl-a on both seasonal and interannual scales, as well as the long-term trends. The phytoplankton Chl-a showed large spatial dynamics with a general decreasing pattern poleward. The seasonal phytoplankton blooms dominated the seasonal characteristics of Chl-a, with spring and fall blooms identified in subpolar waters and single spring blooms in subtropical seas. On interannual scales, we found a Chl-a increasing belt in the subpolar oceans from the marginal sea toward the northeast open ocean waters, with positive trends (~0.02 mg m−3 yr−1, on average) in Chl-a at significant levels (p < 0.05). In the subtropical gyre, Chl-a showed slight but significant negative trends (i.e., <−0.0006 mg m−3 yr−1, at p < 0.05). The negative Chl-a trends in the subtropical waters tended to be driven by the surface warming, which could inhibit nutrient supplies from the subsurface and thus limit phytoplankton growth. For the subpolar waters, although the surface warming also prevailed over the study period, the in situ surface nitrate reservoir somehow showed significant increases in the targeted spots, indicating potential external nitrate supplies into the surface layer. We did not find significant connections between the Chl-a interannual variabilities and the climate indices in the study area. Environmental data with finer spatial and temporal resolutions will further constrain the findings.

Promoting effect of basic metal additives on DeNOx reactions over Pt-based three-way catalysts

Pt has been economically favored over Rh and Pd. However, Pt-based three-way catalysts (TWCs) have been studied less than Pd- and Rh-based TWCs; therefore, their properties have not yet been sufficiently evaluated, especially under conditions relevant to modern three-way catalysis operation, wherein deviations from stoichiometric conditions are often encountered. In this study, we examined the promotional effect of basic metal additives in Pt/M/Al2O3 (M = Ba, La, Sr) on the efficiency of three-way catalytic reactions. The catalytic activities of the Pt/M/Al2O3 catalysts for NO, CO, and total hydrocarbons were superior to those of Pt/Al2O3; moreover, Ba enhanced the catalytic activity of Pt-based catalysts more efficiently than La and Sr. The best-performing catalyst, Pt/Ba/Al2O3, was subjected to kinetic studies and various in situ/operando spectroscopic experiments, namely, X-ray absorption spectroscopy, infrared spectroscopy, and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), to investigate the role of Ba in the NO reduction reaction. The Pt0 species loaded on Ba/Al2O3 were more electron-rich than those loaded on Al2O3, thereby promoting NO dissociation into N and O atoms, as revealed by the AP-XPS results. Moreover, the efficient formation of intermediate surface NOx species, including nitrites and nitrates, and their reactivities toward reductant gases, such as H2 or CO, were critical for promoting the effect of Ba on the NO reduction reaction.

Insight into the promotional mechanism of Cu modification towards wide-temperature NH3-SCR performance of NbCe catalyst

A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst. The best catalyst Cu 0.010 /Nb 1 Ce 3 presented over 90% NO conversion in a wide temperature range of 200−400 o C and exhibited an excellent H 2 O or/and SO 2 resistance at 275 o C. To understand the promotional mechanism of Cu modification, the correlation among the “activity-structure-property” were tried to establish systematically. Cu species highly dispersed on NbCe catalyst to serve as the active component. The strong interaction among Cu, Nb and Ce promoted the emergence of NbO 4 and induced more Brønsted acid sites. And Cu modification obviously enhanced the redox behavior of the NbCe catalyst. Besides, EPR probed the Cu species exited in the form of monomeric and dimeric Cu 2+ , the isolated Cu 2+ acted as catalytic active sites to promote the reaction: Cu 2+ -NO 3 - +NO(g)→Cu 2+ -NO 2 - +NO 2 (g). Then the generated NO 2 would accelerate the fast-SCR reaction process and thus facilitated the low-temperature deNO x efficiency. Moreover, surface nitrates became unstable and easy to decompose after Cu modification, thus providing additional adsorption and activation sites for NH 3 , and ensuring the improvement of catalytic activity at high temperature. Since the NH 3 -SCR reaction followed by E-R reaction pathway efficaciously over Cu 0.010 /Nb 1 Ce 3 catalyst, the excellent H 2 O and SO 2 resistance was as expected.

Low Nitrogen Fixation Related to Shallow Nitracline Across the Eastern Indian Ocean

AbstractThe eastern Indian Ocean (EIO) is characterized by oligotrophic surface water with abundant dust supply, and thus, this environment is considered to provide a favorable niche for cyanobacterial diazotrophs. However, direct measurements have reported low nitrogen fixation with the dominance of heterotrophic diazotrophs, suggesting that the EIO has unique geophysical features and nutrient supplies controlling diazotrophy, in contrast to those in the Atlantic and Pacific Oceans. In this study, we investigated the activity and community of diazotrophs across the EIO from the Bay of Bengal to the west of Australia. Low nitrogen fixation was observed broadly in the EIO (26.1–75.6 μmol N m−2 d−1), except in the west of Australia (82–286 μmol N m−2 d−1). Although the surface nitrate concentration was low in the EIO, the upward nitrate flux was higher because of the shallower nitracline than that in other oligotrophic oceans. This created widespread conditions with low aeFe:N (supply ratio of aerosol iron to nitrogen), resulting in low nitrogen fixation rates. NifH amplicon sequencing demonstrated the dominance of heterotrophic diazotrophs widely in the EIO, with spatial segregation from cyanobacterial diazotrophs (Trichodesmium, UCYN‐A1). In general, cyanobacterial diazotrophs were abundant in the surface waters of the Bay of Bengal and west of Australia with a high aeFe:N supply, whereas heterotrophic diazotrophs were dominant in other broad regions. This finding demonstrates that the shallow nitracline and associated high upward nitrate supply are key factors for the unique diazotrophy in the EIO.

Changes in Soil Properties, Bacterial Communities and Wheat Roots Responding to Subsoiling in South Loess Plateau of China

This study was carried out to investigate effects of subsoiling on the diversity and composition of the bacterial community in a wheat–maize rotation field in the Guanzhong area of Shaanxi Province, China. After the wheat harvest, surface soil samples were collected under two tillage methods (single rotary tillage (RT) and subsoiling + rotary tillage (ST)) to perform high-throughput sequencing and bioinformatics analysis. Soil properties and root length density (RLD) of winter wheat at booting and flowering stages were also studied. Results showed that ST treatment significantly raised the water storage, organic carbon and total nitrogen contents of deep soil (>40 cm), and notably increased the total soil pH, ammonium nitrogen content and RLD in the tillage layer from 0–70 cm at booting stage and 0~100 cm at flowering stage, but the residual nitrate nitrogen significantly decreased by 17.74%. Compared with RT, soil bacterial richness and diversity in the 10~20 cm layer of ST treatment showed a significantly decreased trend. The relative abundances of GAL15, Actinobacteria, Nitrospirae, Rhizobiales, Burkholderiales, Pseudomonas and Serratia in the 10–20 cm layer were remarkably increased in ST. Principal Component Analysis (PCA) and Redundancy Analysis (RDA) results showed that surface soil pH, ammonium nitrogen and nitrate nitrogen contents have the strongest effect on the bacterial structure. In addition, there were positive correlations between the RLD and the relative abundances of Rhizobiales, Burkholderiales, Pseudomonas and the ammonium nitrogen content. In conclusion, although subsoiling was not conducive to improving soil bacterial community richness and diversity, it significantly increased soil beneficial bacteria (biological nitrogen-fixing bacteria, ammonifying bacteria, nitrobacteria) abundances, reduced the nitrogen loss caused by denitrifying bacteria, promoted earlier root development and improved the plant utilization ratio of soil nutrients.

Insight into the Overlooked Photochemical Decomposition of Atmospheric Surface Nitrates Triggered by Visible Light.

The nitrogen oxides (NOx) formed by photochemical reaction of surface nitrates raise significant concerns. However, little is known about the effect of visible light (>380 nm) on nitrate decomposition and the reaction mechanism. Herein, the decomposition of surface nitrates is investigated under visible light. The results indicate that visible light photocatalysis contributes significantly to nitrate decomposition. Monodentate nitrate (m-NO3 - ) can be decomposed into NOx by photogenerated electrons starting from the weakly coordinated N-O bond. Water vapor promotes NOx generation because more stable bidentate nitrate (b-NO3 - ) will be converted into m-NO3 - by surface hydroxyl groups through hydrogen bonding interactions. Alternatively, b-NO3 - can be directly decomposed to NO2 - by NO attack, but this process is subject to photocatalytic oxidation. This work brings a new focus on the atmospheric NOx sources and provides a more nuanced understanding of nitrates decomposition processes.

Insight into the Overlooked Photochemical Decomposition of Atmospheric Surface Nitrates Triggered by Visible Light

AbstractThe nitrogen oxides (NOx) formed by photochemical reaction of surface nitrates raise significant concerns. However, little is known about the effect of visible light (>380 nm) on nitrate decomposition and the reaction mechanism. Herein, the decomposition of surface nitrates is investigated under visible light. The results indicate that visible light photocatalysis contributes significantly to nitrate decomposition. Monodentate nitrate (m‐NO3−) can be decomposed into NOx by photogenerated electrons starting from the weakly coordinated N−O bond. Water vapor promotes NOx generation because more stable bidentate nitrate (b‐NO3−) will be converted into m‐NO3− by surface hydroxyl groups through hydrogen bonding interactions. Alternatively, b‐NO3− can be directly decomposed to NO2− by NO attack, but this process is subject to photocatalytic oxidation. This work brings a new focus on the atmospheric NOx sources and provides a more nuanced understanding of nitrates decomposition processes.

Effect of Support and Pd Cluster Size on Catalytic Methane Partial Oxidation to Dimethyl Ether Using a NO/O2Shuttle

The partial oxidation of methane to dimethyl ether (DME) was studied on palladium supported on SiO2, SiO2-ZrO2, and ZrO2 at 225–375 °C and 0.1 MPa using either O2 or a mixture of NO and O2 as the oxidants. The NO + O2 mixture was more reactive than the O2 toward methane, probably due to the formation of active surface nitrate species. The formation of DME on the catalysts was influenced by the support, with the Pd/ZrO2 catalyst producing DME and the Pd/SiO2 catalyst producing only CO2, irrespective of the oxidant used. The Pd/SiZrO2 catalyst formed DME only when O2 alone was used as the oxidant. For the reaction with NO + O2, in situ Fourier transform infrared (FTIR) measurements showed that the partial oxidation activity on Pd/ZrO2 was related to its ability to form surface-bridged nitrate species, likely due to the presence of basic sites. However, an inhibitory effect of basicity on CH4 turnover frequency (TOF) was attributed to surface nitrate-induced structural modification deduced from X-ray absorption fine structure spectroscopy measurements. For the reaction with only O2, the formation of DME over Pd/ZrO2 and Pd/SiZrO2 was attributed to the reported ability of ZrO2 to retain methoxy intermediates. Furthermore, a weak structural effect on the TOF observed with O2 was attributed to competing effects of decreasing activity for C-H activation and increasing resistance to Pd oxidation with increasing particle size.

Carbon to Nitrogen Uptake Ratios Observed Across the Southern Ocean by the SOCCOM Profiling Float Array

AbstractMeasurements of pH and nitrate from the Southern Ocean Carbon and Climate Observations and Modeling array of profiling floats were used to assess the ratios of dissolved inorganic carbon (DIC) and nitrate (NO3) uptake during the spring to summer bloom period throughout the Southern Ocean. Two hundred and forty‐three bloom periods were observed by 115 floats from 30°S to 70°S. Similar calculations were made using the Takahashi surface DIC and nitrate climatology. To separate the effects of atmospheric CO2 exchange and mixing from phytoplankton uptake, the ratios of changes in DIC to nitrate of surface waters (ΔDIC/ΔNO3) were computed in the Biogeochemical Southern Ocean State Estimate (B‐SOSE) model. Phytoplankton uptake of DIC and nitrate are fixed in B‐SOSE at the Redfield Ratio (RR; 6.6 mol C/mol N). Deviations in the B‐SOSE ΔDIC/ΔNO3 must be due to non‐biological effects of CO2 gas exchange and mixing. ΔDIC/ΔNO3 values observed by floats and in the Takahashi climatology were corrected for the non‐biological effects using B‐SOSE. The corrected, in situ biological uptake ratio (C:N) occurs at values similar to the RR, with two major exceptions. North of 40°S biological DIC uptake is observed with little or no change in nitrate giving high C:N. In the latitude band at 55°S, the Takahashi data give a low C:N value, while floats are high. This may be due to a change in CO2 air‐sea exchange in this region from uptake during the Takahashi reference year of 2005 to outgassing of CO2 during the years sampled by floats.

Adsorption and Oxidation of NO2 on Anatase TiO2: Concerted Nitrate Interaction and Photon-Stimulated Reaction

The catalytic and photon-induced oxidation of NO2 on anatase TiO2 has been studied and compared with the surface nitrate species obtained after adsorption of HNO3. Using a combination of in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), density functional theory (DFT), and temperature-programmed desorption (TPD), it is shown that identical products are obtained in all reaction systems but that their formation rates differ significantly. The surface reaction products are identified as combinations of surface–NO3– species, where NO2 bonds to the lattice oxygen, and freely adsorbed NO3– ions. These products can be obtained either by dissociative adsorption of HNO3 or by catalytic/photocatalytic oxidation of NO2, which is facilitated by UV light. A concerted reaction mechanism is unraveled that involves reorientation of bidentate nitrate that pushes out a neighboring protonated lattice oxygen to form a surface–NO3– species and a terminal OH group. The thermal stability of these surface species has been studied by means of TPD and simultaneous in situ DRIFTS measurements that reveal a main desorption peak (m/z = 46) at around 430 °C, which is attributed to concerted nitrate desorption through pentoxide (N2O5) formation. A weaker and broader TPD peak is found at about 185 °C and is attributed to desorption of nitrate species bonded in a compressed configuration. The experimental results can be explained by the changing stability of the identified nitrate products, which depends strongly on the surface chemical environment and the surface coverage. The DFT results show that the stabilization of intermediate NO2 adsorbates and the final nitrate reaction products occurs through a bifunctional charge exchange mechanism that is mediated by the TiO2 crystal. In particular, a stable surface–NO3– and NO3– ion pair configuration has been identified. This mechanism explains both the thermal and photoinduced oxidation of NO2 and their thermal stability and different formation rates, yielding high photoinduced oxidation reaction rates. Our results provide insights into the structure and chemical stability of nitrate surface products on TiO2 particles and their formation mechanism, which is important for understanding their catalyzed transformation into the harmful compounds HONO and N2O during continued UV light illumination.

Assessing the effect of urbanization on regional-scale surface water-groundwater interaction and nitrate transport

Identifying regional-scale surface water-groundwater interactions (SGI) is vital for predicting anthropogenic effects on surface water bodies and underlying aquifers. However, large-scale water and nutrient flux studies rely on surface water or groundwater-focused models. This study aims to model the effect of urbanization, which is usually accompanied by high groundwater abstraction and surface water pollution, particularly in the developing world, on a regional-scale SGI and nitrate loading. In the study area, the urban expansion increased by over 3% in the last decade. The integrated SWAT-MODFLOW model, Soil and Water Assessment Tool (SWAT) and Modular Finite-Difference Groundwater Flow (MODFLOW) coupling code, was used to assess SGI. By coupling SWAT-MODFLOW with Reactive Transport in 3-Dimensions, the nutrient loading to the river from point and non-point sources was also modeled. Basin average annual results show that groundwater discharge declined with increasing groundwater abstraction and increased with Land use/Land cover (LULC) changes. Groundwater recharge decreased significantly in the Belge season (February to May), and the river seepage and groundwater discharge decreased correspondingly. High spatiotemporal changes in SGI and nitrate loading were found under the combined LULC and groundwater abstraction scenarios. The water yield decreased by 15%. In a large part of the region, the nitrate loading increased by 17–250%. Seasonally controlled groundwater abstraction and water quality monitoring are essential in this region.

Ocean biogeochemistry in the Canadian Earth System Model version 5.0.3: CanESM5 and CanESM5-CanOE

Abstract. The ocean biogeochemistry components of two new versions of the Canadian Earth System Model (CanESM) are presented and compared to observations and other models. CanESM5 employs the same ocean biology model as CanESM2, whereas CanESM5-CanOE (Canadian Ocean Ecosystem model) is a new, more complex model developed for CMIP6, with multiple food chains, flexible phytoplankton elemental ratios, and a prognostic iron cycle. This new model is described in detail and the outputs (distributions of major tracers such as oxygen, dissolved inorganic carbon, and alkalinity, the iron and nitrogen cycles, plankton biomass, and historical trends in CO2 uptake and export production) compared to CanESM5 and CanESM2, as well as to observations and other CMIP6 models. Both CanESM5 models show gains in skill relative to CanESM2, which are attributed primarily to improvements in ocean circulation. CanESM5-CanOE shows improved skill relative to CanESM5 for most major tracers at most depths. CanESM5-CanOE includes a prognostic iron cycle, and maintains high-nutrient/low-chlorophyll conditions in the expected regions (in CanESM2 and CanESM5, iron limitation is specified as a temporally static “mask”). Surface nitrate concentrations are biased low in the subarctic Pacific and equatorial Pacific, and high in the Southern Ocean, in both CanESM5 and CanESM5-CanOE. Export production in CanESM5-CanOE is among the lowest for CMIP6 models; in CanESM5, it is among the highest, but shows the most rapid decline after about 1980. CanESM5-CanOE shows some ability to simulate aspects of plankton community structure that a single-species model can not (e.g. seasonal dominance of large cells) but is biased towards low concentrations of zooplankton and detritus relative to phytoplankton. Cumulative ocean uptake of anthropogenic carbon dioxide through 2014 is lower in both CanESM5-CanOE (122 PgC) and CanESM5 (132 PgC) than in observation-based estimates (145 PgC) or the model ensemble mean (144 PgC).