Influencing factors and significance of organic and inorganic nitrogen isotopic compositions in lacustrine sedimentary rocks

Comprehensive nitrogen biogeochemical cycle has been reconstructed for representative lacustrine organic-rich sedimentary rock in China,namely the Triassic Yanchang Formation(YF,199–230 Ma)in Ordos and the Cretaceous Qingshankou Formation(QF,86–92 Ma)in Songliao basins,by evaluating the organic and inorganic nitrogen isotopic compositions rather than only organic or bulk nitrogen isotopic compositions.The results indicate that the nitrogen isotope values of bulk rock(δ^(15)N_(bulk))in the non-metamorphic stage are significantly different from that of kerogen,which challenge the conceptual framework of sedimentary nitrogen isotope interpretation.Theδ^(15)N_(bulk)from the YF and QF were lower than their respective the nitrogen isotope values of kerogen(δ^(15)N_(ker)),with offsets up to5.1‰,which have the inverse relationship for the metamorphosed rock.Thermal evolution did not significantly modify the d15N of bulk rock and kerogen.The d15N of sediments from the YF(δ^(15)N_(bulk),1.6‰–5.6‰)were lower than that of rock from the QF(δ^(15)N_(bulk),10.2‰–15.3‰).The nitrogen isotope values of silicate incorporated nitrogen(δ^(15)N_(sil))were slightly lower than those of the d15Nker in the YF and obviously lower for the QF.The fact that different nitrogen cycles occur in the YF and QF due to the different depositional redox conditions leads to different isotopic results.The YF water environment dominated by oxic conditions is not conducive to the occurrence of denitrification and anammox,and no abundant N2 loss leads to the relatively lightδ^(15)N_(bulk).In the stratified water for the QF,redox transition zone promotes denitrification and anammox,resulting in the heavyδ^(15)N_(bulk)of rock and promotes the DNRA,resulting in heavyδ^(15)N_(ker)and lowδ^(15)N_(sil).

Isotope constraints on seasonal dynamics of nitrogen in Zhanjiang Bay, a typical mariculture bay in South China

Eutrophication in coastal waters has been increasing remarkably,severely impacting the water quality in mariculture bays.In this study,we conducted multiple isotopic measurements on suspended particulate nitrogen(δ^(15)N-PN) and dissolved nitrate(δ^(15)N-NO_(3)^(-)and δ^(18)O-NO_(3)^(-)) in Zhanjiang Bay,a typical mariculture bay with a high level of eutrophication in South China,to investigate the changes in nitrogen sources and their cycling between the rainy and dry seasons.During the rainy season,the study found no significant relation between δ^(15)NPN and δ^(15)N-NO_(3)^(-)due to the impact of heavy rainfall and terrestrial erosion.In the upper bay,a slight nitrate loss and slightly higher δ_(15)N-NO_(3)^(-)and δ^(18)O-NO_(3)^(-)values were observed,attributed to intense physical sedimentwater interactions.Despite some fluctuations,nitrate concentrations in the lower bay mainly aligned with the theoretical mixing line during the rainy season,suggesting that nitrate was primarily influenced by terrestrial erosion and that nitrate isotopes resembled the source.Consequently,the isotopic values of nitrate can be used for source apportionment in the rainy season.The results indicated that soil nitrogen(36%) and manure and sewage(33%) were the predominant nitrogen sources contributing to nitrogen loads during this period.In contrast,the dry season saw a deficient ammonium concentration(<0.2 μmol/L) in the bay,due to nearly complete consumption by phytoplankton during the red tide period.Additionally,the significant loss of nitrate and simultaneous increase in the stable isotopes of dissolved and particulate nitrogen suggest a strong coupling of assimilation and mineralization during the dry season.More active biogeochemical processes during the dry season may be related to decreased runoff and increased water retention time.Overall,our study illustrated the major seasonal nitrogen sources and their dynamics in Zhanjiang B ay,providing valuable insights for formulating effective policies to mitigate eutrophication in mariculture bays.

Tracing nitrate sources in one of the world's largest eutrophicated bays(Hangzhou Bay):insights from nitrogen and oxygen isotopes

Eutrophication caused by inputs of excess nitrogen(N) has become a serious environmental problem in Hangzhou Bay(China),but the sources of this nitrogen are not well understood.In this study,the August 2019 distributions of salinity,nutrients [nitrate(NO_(3)^(-)),nitrite,ammonium,and phosphate],and the stable isotopic composition of NO_(3)^(-)(δ^(15)N and δ^(18)O) were used to investigate sources of dissolved inorganic nitrogen(DIN) to Hangzhou B ay.Spatial distributions of nitrate,salinity,and nitrate δ^(18)O indicate that the Qiantang River,the Changjiang River,and nearshore coastal waters may all contribute nitrate to the bay.Based on the isotopic compositions of nitrate in these potential source waters and conservative mixing of nitrate in our study area,we suggest that the NO_(3)^(- )in Hangzhou B ay was likely derived mainly from soils,synthetic N fertilizer,and manure and sewage.End-member modeling indicates that in the upper half of the bay,the Qiantang River was a very important DIN source,possibly contributing more than 50% of DIN in the bay head area.In the lower half of the bay,DIN was sourced mainly from strongly intruding coastal water.DIN coming directly from the Changjiang River made a relatively small contribution to Hangzhou Bay DIN in August 2019.

Nitrogen isotope stratigraphy of the Early Cambrian successions in the Tarim Basin:Spatial variability of nitrogen cycling and its implication for paleo-oceanic redox conditions

The Early Cambrian represents a critical time period characterized by extraordinary biological innovations and dynamic redox conditions in seawaters.Nitrogen isotopic signatures of ancient sediments have the potential to elucidate the evolutionary path of marine redox states and the biogeochemical nitrogen cycle within the water column of the Early Cambrian ocean.While existing research on this topic has predominantly focused on South China,the exploration of other continental margins has been limited,leaving contradictory hypotheses untested.In this study,pairedδ^(15)N andδ^(13)C org analyses were performed on the Lower Cambrian successions from the Shiairike section(inner ramp)and Well Tadong 2(deep shelf/basin)in the northwestern and eastern Tarim Basin,respectively.Our data from the Shiairike section reveal a discernible shift in the operation of different nitrogen cycles for the black chert-shale unit,also referred to as the black rock series in Chinese literature,of the Yurtus Formation(Fortunian stage to lower Stage 3).Oscillatingδ^(15)N values for its lower part are suggestive of alternating anaerobic assimilation of NH 4+and denitrification/anammox.This is likely attributed to a shallow,unstable chemocline consistent with the upwelling and incursion of deep,anoxic waters during a major transgression.In contrast,aerobic nitrogen cycling,indicated by positiveδ^(15)N values of>2‰,dominated the upper part alongside a reduction in upwelling intensity.On the other hand,theδ^(15)N signatures of Xishanbulake and Xidashan Formations of Well Tadong 2,which encompass a time interval from the Cambrian Fortunian Age to Age 4,are indicative of N_(2)fixation by diazotrophs as the major nitrogen source.The two studied intervals,although not time-equivalent,exhibit separated states of nitrogen cycling at least during the deposition of the Yurtus black rock series.The spatially different nitrogen cycling of the studied sections is compatible with a redox-stratified ocean during the deposition of the Yurtus black rock series.The build-up of a NO_(3)−reservoir and aerobic nitrogen cycling in seawater was largely restricted to near-shore settings whereas anaerobic nitrogen cycling dominated by N_(2)fixation served as the main nitrogen uptake pathway in off-shore settings.

Spatial distributions of organic carbon and nitrogen and their isotopic compositions in sediments of the Changjiang Estuary and its adjacent sea area

The spatial distribution patterns of total organic carbon and total nitrogen show significant correlations with currents of the East China Sea Shelf. Corresponding to distributions of these currents, the study area could be divided into four different parts. Total organic carbon, total nitrogen, and organic carbon and nitrogen stable isotopes in sediments show linear correlations with mean grain size, respectively, thus ＂grain size effect＂ is an important factor that influences their distributions. C/N ratios can reflect source information of organic matter to a certain degree. In contrast, nitrogen stable isotope shows different spatial distribution patterns with C/N and organic carbon stable isotope, according to their relationships and regional distributions. The highest contribution （up to 50%） of terrestrial organic carbon appears near the Changjiang Estuary with isolines projecting towards northeast, indicating the influence of the Changjiang dilution water. Terrestrial particulate organic matter suffers from effects of diagenesis, benthos and incessant inputting of dead organic matter of plankton, after depositing in seabed. Therefore, the contribution of terrestrial organic carbon to particulate organic matter is obviously greater than that to organic matter in sediments in the same place.

Atmospheric nitrogen deposition in Yangtze River Delta:insights gained from the nitrogen content and isotopic composition of the moss Haplocladium microphyllum

Simple and inexpensive estimation of the rates and sources of atmospheric nitrogen(N)deposition is critical for its effective mitigation in a region with different land-use types.In this study,the N content and N isotopic composition(δ15N)of moss(Haplocladium microphyllum)tissues and precipitation at six sites with three land-use types(urban,suburban,and rural)were measured in the Yangtze River Delta.A significant linear relationship between moss N content and wet N deposition,and a consistent decrease trend for moss N content and wet N deposition from urban to suburban to rural areas were observed.More negativeδ15N of suburban and rural mosses indicated N mainly released from agriculture and effluent,while the less negativeδ15N of urban mosses were mainly influenced by fossil fuel combustion and traffic emissions.Although the negative mossδ15N indicates that reduced N dominates wet N deposition,there was no significant correlation between mossδ15N and the ratio of ammonium to nitrate(NH4+/NO3−).These results reveal that the moss N content andδ15N can be used as a complementary tool for estimating the rates and sources of wet N deposition in a region with different land-use types.

Nitrogen Isotopic Fractionation Related to Nitrification Capacity in Agricultural Soils

A laboratory-based aerobic incubation was conducted to investigate nitrogen （N） isotopic fractionation related to nitrification in five agricultural soils after application of ammonium sulfate （（NH4）2804）. The soil samples were collected from a subtropical barren land soil derived from granite （RGB）, three subtropical upland soils derived from granite （RQU）, Quaternary red earth （RGU）, Quaternary Xiashu loess （YQU） and a temperate upland soil generated from alluvial deposit （FAU）. The five soils varied in nitrification potential, being in the order of FAU 〉 YQU 〉 RGU 〉 RQU 〉 RGB. Significant N isotopic fractionation accompanied nitrification of NH4＋. 615N values of NH4＋ increased with enhanced nitrification over time in the four upland soils with NH4＋ addition, while those of NO3 decreased consistently to the minimum and thereafter increased. 515N values of NH4＋ showed a significantly negative linear relationship with NH4＋-N concentration, but a positive linear relationship with NO3-N concentration. The apparent isotopic fractionation factor calculated based on the loss of NH4＋ was 1.036 for RQU, 1.022 for RGU, 1.016 for YQU, and 1.020 for FAU, respectively. Zero- and first-order reaction kinetics seemed to have their limitations in describing the nitrification process affected by NH4＋ input in the studied soils. In contrast, N kinetic isotope fractionation was closely related to the nitrifying activity, and might serve as an alternative tool for estimating the nitrification capacity of agricultural soils.

Sources and transformations of nitrite in the Amundsen Sea in summer 2019 and 2020 as revealed by nitrogen and oxygen isotopes

In this study,the nitrogen and oxygen isotope compositions of nitrite in the upper 150 m water column of the Amundsen Sea in the summer of 2019 and 2020 were measured to reveal the distribution and transformation of nitrite in the euphotic zone of the Southern Ocean.We found that primary nitrite maxima(PNMs)are widely present in the Amundsen Sea,where the depth of occurrence deepens from east to west and nitrite concentrations increases.Evidence from dual isotopes suggests that the formation of PNMs in all regions of the Amundsen Sea is dominated by ammonia oxidation.More importantly,the nitrogen and oxygen isotope compositions of nitrite in the Amundsen Sea mixed layer are abnormal,and their depth profiles are mirror symmetrical.Isotopic anomalies exhibit spatial variations,with central surface water having the lowest nitrogen isotope composition(−89.9‰±0.2‰)and western surface water having the highest oxygen isotope composition(63.3‰±0.3‰).Isotopic exchange reaction between nitrate and nitrite is responsible for these isotope anomalies,as both nitrogen and oxygen isotopes have large isotopic fractionation and opposite enrichment effects.This proves that isotopic exchange reaction operates extensively in different regions of the Amundsen Sea.Our study highlights the unique role of dual isotopes of nitrite in deepening the understanding of nitrogen cycle.Further studies on ammonia oxidation and isotopic exchange between nitrate and nitrite are warranted in the future to understand their roles in the nitrogen cycle in the Southern Ocean.

Nitrogen Contents and Isotopic Characteristics of Mesozoic and Cenozoic Granites in Northeastern China

The method of determining the nitrogen isotopic composition of granites in the northeastern part of China is described. The content and isotopic values of nitrogen released from granite samples by stepwise heating were determined as well. The results showed that the different areas of northeastern China have a great difference in nitrogen content and isotopic composition. Nitrogen released from the granites is 1.64-6.23μL/g, with the maximum at about 600℃; from rhyolite and granophyre is 108.98-755.96μL/g, with the maximum at about 900℃. It is proved that fluid is characterized by heterogeneity in the deep crust of the different areas in northeastern China. The nitrogen isotopic compositions in different ranges of temperatures are weighted. And the nitrogen isotopic values are +9.2‰ to +17.0‰, with a variation range of 7.8‰. The nitrogen isotopic ratios may have been fractionated during degassing and the fluid released from granites is the residual component.

Nitrogen uptake and transfer in broad bean and garlic strip intercropping systems

Utilization and transfer of nitrogen （N）in a strip intercropping system of garlic （Allium safivum L.） and broad bean （Vicia faba L.） have been investigated rarely. The objectives of this study were to quantify N uptake and utilization by intercropped broad bean and garlic and determine the magnitude of N transfer from broad bean to garlic. Field and pot trials were carried out in the Erhai Lake Basin in China using ^15N tracer applied to the soil or injected into broad bean plants. Strip intercropping of garlic and broad bean increased N absorption （47.2%） compared with sole crop broad bean （31.9%） or sole crop garlic （40.7%） and reduced soil residual N. Nearly 15% of 15N injected into petioles of broad bean intercropped with garlic was recovered in garlic at harvest, suggesting that N could be transferred from broad bean to strip intercropped garlic. The findings provide a basis for evaluating legumes＇ role in optimizing N fertilization when intercropped with non-legumes.

Sources of particulate organic matter in the Chukchi and Siberian shelves: clues from carbon and nitrogen isotopes

The stable isotopic composition(δ13C andδ15N)and carbon/nitrogen ratio(C/N)of particulate organic matter(POM)in the Chukchi and East Siberian shelves from July to September,2016 were measured to evaluate the spatial variability and origin of POM.Theδ13CPOC values were in the range of−29.5‰to−17.5‰with an average of−25.9‰±2.0‰,and theδ15NPN values ranged from 3.9‰to 13.1‰with an average of 8.0‰±1.6‰.The C/N ratios in the East Siberian shelf were generally higher than those in the Chukchi shelf,while theδ13C andδ15N values were just the opposite.Abnormally low C/N ratios(<4),lowδ13CPOC(almost−28‰)and highδ15NPN(>10‰)values were observed in the Wrangel Island polynya,which was attributed to the early bloom of small phytoplankton.The contributions of terrestrial POM,bloom-produced POM and non-bloom marine POM were estimated using a three end-member mixing model.The spatial distribution of terrestrial POM showed a high fraction in the East Siberian shelf and decreased eastward,indicating the influence of Russian rivers.The distribution of non-bloom marine POM showed a high fraction in the Chukchi shelf with the highest fraction occurring in the Bering Strait and decreased westward,suggesting the stimulation of biological production by the Pacific inflow in the Chukchi shelf.The fractions of bloom-produced POM were highest in the winter polynya and gradually decreased toward the periphery.A negative relationship between the bloom-produced POM and the sea ice meltwater inventory was observed,indicating that the net sea ice loss promotes early bloom in the polynya.Given the high fraction of bloom-produced POM,the early bloom of phytoplankton in the polynyas may play an important role on marine production and POM export in the Arctic shelves.

Organic carbon and nitrogen isotopes in surface sediments from the western Arctic Ocean and their implications for sedimentary environments

Surface sediments from the Chukchi Sea and adjacent arctic deep sea were investigated for organic carbon and nitrogen isotopes （in δ13Corg and δ15Norg） as well as biogeni＇c silica （BSiO2）. δ13Corg and δ15Norg values of surface sediments in the study area fall between the end-member values of marine and terrestrial organic matter from the surrounding lands and seas, their variations reflect the changes of marine productivity and terrestrial supply in the study area. BSiO2 shows a similar distribution pattern with δ13Corg and δ15Norg, and can be used as an indicator of marine productivity. In the central-west Chukchi Sea and the Chukchi Rise, sediments have higher δ13Corg, δ15Norg and BSiO2 values, indicating the region has high marine productivity influenced by the nutrient-rich branches of the Pacific waters. In the coastal zone off northwestern Alaska, δ13Corg and δ15Norg values become lighter, indicating a weakening marine productivity and an increasing terrigenous supply due to the effects of the least nutrient-rich branch of the Pacific waters. In the north and the northeast of the study area （including the Chukchi Plateau, the Canada Basin and the Beaufort shelf）, δ13Corg, δ15Norg and BSiO2 have the lowest values, and the terrigenous organic matter becomes dominant in surface sediments because this region has the longest ice-covered duration, the least nutrient-rich seawater and the increasing supply of terrestrial materials from the Mackenzie River and the northern Alaska under the action of the clockwise Beaufort gyre. Because the subarctic Pacific waters are continuously discharged into the central basin of the Arctic Ocean through the study area, the nutrient pool in the Chukchi Sea can be considered as a typical open system, the ratio of δ15Norg to BSiO2 content show some tracers that the level of nutrient utilization is contrary to nutrient supply and marine productivity formed in seawater.

Analyzing biases of nitrogen contents and δ^(15)N values arising from acidified marine sediments with different CaCO_3 concentrations

In some studies, the researchers pretreated and measured organic carbon, nitrogen and their isotopes（δ^（13）C and δ^（15）N） of marine sediment together, to save costs and resources of analysis. However, the procedure of acidification to remove inorganic carbon for analysing δ^（13）C can affect the values of nitrogen and δ^（15）N, and the biases vary a lot depending on the CaCO_3 contents of sediments. In this study, the biases of total nitrogen（TN）and δ^（15）N values arising from acidified sediments were compared between the CaCO_3-poor（1%–16%） and CaCO_3-rich（20%–40%） samples. TN and δ^（15）N values were altered during acid treatment（without centrifugation） that possibly led to N-containing compounds volatilization. For CaCO_3-poor samples, acidification led to a range of 0%–40% TN losses and 0‰–2‰ shift in δ^（15）N values; and 10%–60% TN losses and 1‰–14‰ shift in δ^（15）N values for CaCO_3-rich samples. The biases from most samples exceeded the precision of the instrument（0.002% for TN and 0.08‰ for δ^（15）N）, and high biases could mislead our judgment for the environmental implication of the data. Thus,avoiding co-analysis of organic carbon, nitrogen and their isotopes（δ^（13）C and δ^（15）N） in sediments, even for CaCO_3-poor marine sediments, is necessary.

Impact of an accidental explosion in Tianjin Port on enhanced atmospheric nitrogen deposition over the Bohai Sea inferred from aerosol nitrate dual isotopes

In recent years,emergent pollutant’s accidents have occurred frequently in China,causing serious harm to the ecological environment.In this study,the impact of an accidental fire and explosion at Tianjin Port in 2015 on the atmosphere over the Bohai Sea was explored.Results showed sharp increases in the concentrations of several important components of fine particulate matter(e.g.NO3−,SO42−,NH4+,organic carbon,elemental carbon)over Beihuangcheng Island after the explosion.Among them,NO3−was most affected(about 10 days),with a maximum concentration of 16.45μg m−3.Theδ15N-NO3−ranged from−1.58‰to+8.74‰,with an average of+2.79‰±3.32‰.Influenced by the explosion,δ15N-NO3−decreased significantly,which was in accordance with the industrial processes of explosives.Theδ18O-NO3−varied between+49.40‰and+69.52‰,and showed a marked increase(+66.62‰±3.92‰)in the explosion-affected period.Using Monte Carlo simulation,the•OH pathway for NO3−formation was 51.79%±10.94%at that time—much lower than in the regular period.The elevated dry deposition of NO3−caused by the explosion was 266.08μmol N m−2 d−1 over the Bohai Sea—again,much higher than in the regular period.With the dry nitrogen deposition of NH4+(42.41μmol N m−2 d−1),the total nitrogen deposition increased by 308.49μmol N m−2 d−1,leading to severe ecological risk.Through the inverse computation of the dry deposition flux of NO3−,the affected area over the Bohai Sea was less than 1.42×104 km2,which is about 20%of the total area.

Sewage pollution in Negril, Jamaica: effects on nutrition and ecology of coral reef macroalgae

Coral reefs in the Negril Marine Park （NMP）, Jamaica, have been increasingly impacted by nutrient pollution and macroalgal blooms following decades of intensive development as a major tourist destination. A baseline survey of DIN and SRP concentrations, C：N：P and stable nitrogen isotope ratios （δ^15N） of abundant reef macroalgae on shallow and deep reefs of the NMP in 1998 showed strong P-limitation and evidence of increasing sewage pollution. In 1999, a sewage collection and treatment project began diverting wastewater from the resort and urban areas to a pond system that discharged partially-treated effluent into the South Negril River （SNR）. These sewage discharges significantly increased concentrations of NH2 and SRP （N：P -13） in the SNR, which flows into Long Bay and around Negril＇s ＂West End＂. Concentrations of SRP, the primary limiting nutrient, were higher on shallow reefs of the West End in 2001 compared to 1998. Stable nitrogen isotope ratios （δ^15N） of abundant reef macroalgae on both shallow and deep reefs of the West End in 2002 were significantly higher than baseline values in 1998, indicating an escalating impact of sewage nitrogen pollution over this timeframe. The increased nutrient concentrations and δ^15N enrichment of reef macroalgae correlated with blooms of the chlorophyte Chaetornorpha linum in shallow waters of Long Bay and Codium isthrnocladum and Caulerpa cupressoides on deep reefs of the West End. Sewage treatment systems adjacent to coral reefs must include nutrient removal to ensure that DIN and SRP concentrations, after dilution, are below the low thresholds noted for these oligotrophic ecosystems.

Nitrate δ^(15)N and δ^(18)O evidence for active biological transformation in the Changjiang Estuary and the adjacent East China Sea

The Changjiang Estuary has been considered as one of the most polluted estuaries in the world due to high nitrate （NO3） input, especially in spring and summer. In this study, 6~5N and t^180 of NO3, along with other chemical parameters in this area, were measured in spring to evaluate NO3 biogeochemical processes. A simple two end-members mixing model was used to examine the relative contribution of the Changjiang River Diluted Water and marine water to NO~ sources in the Changjiang Estuary and the adjacent East Chi- na Sea. The isotopic signals show that NO3 behaved relatively and conservatively in Transect F and Transect P where assimilation was weak possibly due to vertical mixing, while active assimilation and weak nitrifi- cation occurred in Transect D. Spatial difference in assimilation was indicated by the ~ 1：1 enrichment of S 15N and 6180 in the three transects, while spatial difference in nitrification was reflected by deviations of 15N and 6180 from assimilation line. Our results suggest that the input of the Changjiang River Diluted Wa- ter promoted NO3 assimilation possibly by stratifying the water column which favored the phytoplankton growth.

Food web structure and trophic levels in polyculture ricecrab fields

Stable carbon and nitrogen isotopes were used to investigate nutrient pathways and trophic relationships from the rice-crab system in Panjin, Liaoning Province, China. Values of 313C ranged from -27.38%±0.44%o to -18.34%±0.26%o and δ^15N ranged from 1.10%o4-0.88%o to 9.33%±0.57%. Pseudorasbora parva （Stone moroko） had the highest δ^13C and 8tSN values. The lowest δ^13C values were obtained for the macrophytes and the lowest δ^15N value was found in sediments. Stable carbon and nitrogen isotopes were used to determine the contribution of different food items to the diets of crabs. The δ^13C results indicated that the Pseudorasbora parva made the greatest contribution to the diet of Eriocheir sinensis （Chinese mitten crab）, while the δ^15N results indicated that most food items contributed more than 10% to the diet of the crab. There were three trophic levels identified in the system （Levels 0-2）. The crab Eriocheir sinensis, fish Pseudorasbora parva and Misgurnus anguillicaudatus （Oriental weatherfish）, and the oligochaete Limnodrilus hoffmeisteri （Limnodrilus worm）, were at the second level, zooplankton were at the first level and suspended particulate matter and macrophytes were at trophic position 0.

Characteristics of the δ15NNO3 distribution and its drivers in the Changjiang River estuary and adjacent waters

In this study, we conducted investigations in the Changjiang （Yangtze） River estuary and adjacent waters （CREAW） in June and November of 2014. We collected water samples from different depths to analyze the nitrogen isotopic compositions of nitrate, nutrient concentrations （including inorganic N, P, and Si）, and other physical and biological parameters, along with the vertical distribution and seasonal variations of these parameters. The compositions of nitrogen isotope in nitrate were measured with the denitrifier method. Results show that the Changjiang River diluted water （CDW） was the main factor affecting the shallow waters （above 10 m） of the CREAW, and CDW tended to influence the northern areas in June and the southern areas in November. 615Nrqo~ values in CDW ranged from 3.21%o-3.55%o. In contrast, the deep waters （below 30 m） were affected by the subsurface water of the Kuroshio Current, which intruded into the waters near 3 I^N in June. The ~iI^NNo3 values of these waters were 6.03%0-7.6%0, slightly higher than the values of the Kuroshio Current. Nitrate assimilation by phytoplankton in the shallow waters of the study area varied seasonally. Because of the favorable temperature and nutrient conditions in June, abundant phytoplankton growth resulted in harmful algae blooms （HABs）. Therefore, nitrate assimilation was strong in June and weak in November. The ~15NNo3 fractionations caused by assimilation of phytoplankton were 4.57%0 and 4.41%o in the shallow waters in June and November, respectively. These results are consistent with previous laboratory cultures and in situ investigations. Nitrification processes were observed in some deep waters of the study area, and they were more apparent in November than in June. The fractionation values of nitrification ranged from 24%0-25%o, which agrees with results for Nitrosospira tenuis reported by previous studies.

Tree-ring δ^(15)N of Qinghai spruce in the central Qilian Mountains of China:Is pre-treatment of wood samples necessary?

A knowledge of the tree-ring stable nitrogen isotope ratio(δ^(15)N)can deepen our understanding of forest ecosystem dynamics by indicating the long-term availability,cycling and sources of nitrogen(N).However,the radial mobility of N blurs the interannual variations in the long-term N records.Previous studies of the chemical extraction of tree rings before analysis had produced inconsistent results and it is still unclear whether it is necessary to pre-treat wood samples from specific tree species to remove soluble N compounds before determining theδ^(15)N values.We compared the effects of pre-treatment with organic solvents and hot ultrapure water on the N concentration andδ^(15)N of tree rings from endemic Qinghai spruce(Picea crassifolia)growing in the interior of the central Qilian Mountains,China,during the last 60 a.We assessed the effects of different preparation protocols on the removal of the labile N compounds and investigated the need to pre-treat wood samples before determining theδ^(15)N values of tree rings.Increasing trends of the tree-ring N concentration were consistently observed in both the extracted and unextracted wood samples.The total N removed by extraction with organic solvents was about 17.60%,with a significantly higher amount in the sapwood section(P<0.01).Theδ^(15)N values of tree rings decreased consistently from 1960 to 2019 in both the extracted and unextracted wood samples.Extraction with organic solvents increased theδ^(15)N values markedly by about 5.2‰and reduced the variations in theδ^(15)N series.However,extraction with hot ultrapure water had little effect,with only a slight decrease in theδ^(15)N values of about 0.5‰.Our results showed that the radial pattern in the inter-ring movement of N in Qinghai spruce was not minimized by extraction with either organic solvents or hot ultrapure water.It is unnecessary to conduct hot ultrapure water extraction for the wood samples from Qinghai spruce because of its negligible effect on the removal of the labile N.Theδ^(15)N variation trend of tree rings in the unextracted wood samples was not influenced by the heartwood-sapwood transition zone.We suggest that theδ^(15)N values of the unextracted wood samples of the climate-sensitive Qinghai spruce could be used to explore the ecophysiological dynamics while focusing on the long-term variations.

Coupled δ^(15)N_(TN) and δ^(13)C_(TOC) Insights into Methane Seepage Activities in Bulk Marine Sediments of the Qiongdongnan Basin, South China Sea

Recently,methane seepage related to the dissociation of natural gas hydrates has attracted much attention,which has a significant impact on the study of the global carbon and nitrogen cycles.Based on the detailed geochemical analyses of sediments(core Q6)from the Qiongdongnan Basin,South China Sea,three methane seepage activities were identified and the exact horizons of anaerobic oxidation of methane(AOM)were defined.Furthermore,organic carbon isotopic(δ^(13)C_(TOC))levels ranged from−23.6‰–−20.6‰PDB;nitrogen isotopes(δ^(15)N_(TN))of the same sedimentary samples ranged from 1.8‰–5.3‰.We also found obvious simultaneous negative excursions of organic carbon isotopes(δ^(13)C_(TOC))and nitrogen isotopes(δ^(15)N_(TN))in the horizons of methane seepages.Compared with the normal sediments,their maximum negative excursions were 2.6‰and 2.5‰,respectively.We discuss in detail the various characteristics ofδ^(15)N_(TN) andδ^(13)C_(TOC) levels in sediments and their coupling responses to methane seepage activities.We believe that the methane seepage events changed the evolution trajectory ofδ^(15)N_(TN) andδ^(13)C_(TOC) levels in sediment records,which resulted in the simultaneous negative excursions.This phenomenon is of great significance to reveal the historical dissociation of natural gas hydrates and their influence on the deep-sea carbon and nitrogen pool.