Progress in the Study of Marine Stable Nitrogen Isotopic Changes and Its Geological Records

Marine stable nitrogen isotope containing much key biogeochemical information, is an important way in identifying marine nitrogen sources and understanding the marine nitrogen cycles. These isotopic signals can be preserved in marine sediments and used to trace the marine biogeochemical cycles and environment changes during geological history. Studies in recent decades have illustrated the key role of nitrogen fixation and denitrification. Because of the spatiotemporal variability and the complexity of ocean processes and nitrogen sources in the marine environment, we need to combine the modern observations with geological records, integrate oceanography, biology, and geology, and consider the hydrological environment, geological processes and climate changes, to understand the coupling between the ocean nitrogen cycle, climate and environmental changes.     

Soil water movement and nutrient cycling in semi-arid rangeland: vegetation change and system resilience

Recent decades have seen rapid intensification of cattle production in semi-arid savannah ecosystems, increasingly on formalized ranch blocks. As a result, vegetation community changes have occurred, notably bush encroachment (increased bush dominance) in intensively grazed areas. The exact causes of this vegetation change remain widely debated. Previous studies have suggested: (i) increased leaching of water and nutrients into the subsoil in intensively grazed areas provides deeper rooting bush species with a competitive advantage for soil water and nutrients, and (ii) nutrient leaching may be exacerbated by nutrient inputs from cattle dung and urine. Our research in the Eastern Kalahari showed that in infertile sandy soils both the magnitude of soil water and concentration of soil nutrients leached into the subsoil is largely unaffected by the ecological and biochemical effects of increased cattle use. We found that despite the high soil hydraulic conductivity ( &greaterno;12 cm h⁻¹), relatively high subsoil moisture contents and the restriction of water movement to matrix flow pathways prevent leaching losses beyond the rooting zone of savannah grass species. No significant differences in patterns of soil water redistribution were noted between bush dominant and grass dominant sites. We also found that the low nutrient status of Kalahari soils and leachate movement as matrix flow combine to allow nutrient adsorption on to soil particles. Nutrient adsorption ensures that nitrogen and phosphorus cycling remains topsoil dominated even following the removal of vegetation and direct nutrient inputs in cattle dung and urine. This conclusion refutes environmental change models that portray increases in the leaching of soil water and available nitrogen as a major factor causing bush encroachment. This provides a possible explanation for the now widely cited, but hitherto unexplained, resilience of dryland soils. We suggest that infertile sandy soils appear resilient to changes in soil water distribution and nutrient availability caused by increased cattle use. Hence, soil characteristics contribute to the resilience to permanent ecological change that is increasingly recognized as an attribute of semi-arid rangelands. © 1998 John Wiley & Sons, Ltd.     

Cymrite as mineral clathrate: An overlooked redox insensitive transporter of nitrogen in the mantle

We study the phase relations and mineral chemistry in the systems muscovite–NH₃–N₂-H₂O and eclogite + muscovite–NH₃–N₂-H₂O at 6.3–7.8 GPa, 1000–1200 °C, and oxygen fugacity (fO₂) from ∼IW (Fe–FeO) to ∼ NNO (Ni–NiO) equilibria. The quenched H₂O-bearing fluids differ in nitrogen speciation from NH₃-rich to N₂–rich, and the respective N₂/(NH₃+N₂) ratio varies from <0.1 to ∼ 1. N-bearing K-cymrite is obtained in association with a kyanite-garnet-jadeite ± muscovite ± corundum assemblage in the muscovite–NH₃–N₂-H₂O system and coexists with pyrope-almandine garnet and omphacite in the eclogite + muscovite–NH₃–N₂-H₂O system. The presence of an N-bearing fluid in the studied systems stabilizes the K-cymrite structure. Muscovite does not convert to K-cymrite in the absence of NH₃–N₂-bearing fluid up to 7.8 GPa and 1070–1120 °C. According to FTIR and Raman spectroscopy, K-cymrite in equilibrium with an N-rich fluid can capture a huge amount of nitrogen in cages of its framework, mainly as N₂ molecules at fO₂ ∼NNO and predominantly as NH₃ molecules at fO₂ ∼IW. The storage capacity of K-cymrite with respect to nitrogen increases from 2.9 to 6.3 wt% with increase of fO₂. FTIR spectroscopy of muscovite equilibrated with K-cymrite shows that the clathrate mechanism of nitrogen entrapment by aluminosilicates (as neutral N₂ and NH₃ molecules) is much more efficient than the K⁺ → (NH₄)⁺ substitution. The structure of N-bearing K-cymrite (K,(NH₄⁺))[AlSi₃O₈]·(N₂,NH₃,H₂O) determined using X-ray single-crystal diffraction is very similar to that of H₂O-bearing K- and Ba-cymrites. It includes aluminosilicate layers consisting of double six-membered tetrahedral rings and cation sites statistically occupied with K⁺, Ba²⁺ and (NH₄)⁺ on the six-fold symmetry axis in interlayer space. The N₂ and NH₃ molecules are located near the cage centers and, unlike H₂O molecules, are included in the coordination environment of the cations. Our study confirms that NH₃- and N₂-rich K-cymrite may be stable in metapelites and can act as a redox insensitive carrier of nitrogen to >250 km mantle depths in downgoing slabs. The stability field of N-rich K-cymrite in the presence of an N₂–H₂O–NH₃-bearing fluid is inferred to be P ≥ 4 GPa in metasediments rich in K-feldspar and P ≥ 6 GPa in those containing phengite. As the slab material sinks deeper than 250–300 km where N-bearing K-cymrite may lose stability, the releasing nitrogen may migrate to metal-saturated mantle and become stored there in γ−Fe, Fe₃C, metal melt, or even iron nitride phases.     

Nitrogen Mass Fraction and Stable Isotope Ratios for Fourteen Geological Reference Materials: Evaluating the Applicability of Elemental Analyser Versus Sealed Tube Combustion Methods

Thirteen commercially available silicate reference materials (RM) and one in‐house reference material, eleven of which have no previously published values, were analysed for nitrogen mass fraction and isotopic ratios with an Elemental Analyser (EA), and a Sealed Tube Combustion line, coupled to a continuous flow isotope ratio mass spectrometer (IRMS). These materials ranged from < 10 μg g^?1 to 1% m/m nitrogen mass fractions and δ¹⁵N of ?0.5 to +19.8‰. Existing nitrogen RM BHVO‐2, MS#5 and SGR‐1b were used to assess the accuracy of the data from the sealed tube combustion line, which was found to be in good agreement with existing published values. In contrast, the EA‐IRMS failed to fully liberate nitrogen from all silicate rocks and minerals (achieving a mean of 44 ± 10% nitrogen yield) resulting in kinetic fractionation of isotope values by ?1.4‰ on average. Therefore, sealed tube combustion is better suited for analyses of silicate‐bound nitrogen. The EA worked reliably for organic samples, but care should be taken when using the EA for silicate nitrogen research. Moving forward, it is recommended that BHVO‐2, Biotite‐Fe, FK‐N and UB‐N be used as quality control materials as they appear to be most reproducible in terms of nitrogen mass fraction (relative error < 10%, 1s), and isotopic composition (< 0.6‰, 1s).     

长江口邻近海域氮同位素的周日变化特征及其对营养盐过程的指示

长江口邻近海域的氮循环过程一直是近海富营养化研究领域的热点问题, 然而目前较少有针对短周期的调查研究。本文调查了该区域氮、磷、硅等主要营养盐及多种形态的氮稳定同位素的在潮周期周日变化特征。结果显示, NO_3~-、NH_4~+、PO_4~(3-)和SiO_3~(2-)的浓度范围分别为 14.09—55.85、0.21—2.26、0.82—1.08 和 16.80—33.85μmol/L, 而δ~(15)N-NO_3~-、δ~(18)O-NO_3~-、δ~(15)N_P和δ~(13)C_P 等的分布范围分别为 4.7‰—11.1‰、-2.0‰—7.8‰、-1.2‰—7.9‰和-22.9‰— -14.7‰。NO_3~-、PO_4~(3-)和SiO_2~(3-)均与盐度呈现明显的负相关特征, 说明三者的主要来源为长江冲淡水; 4NH(10)则随盐度升高而浓度增加, 且在底层高浓度出现时刻与高盐水团输入时刻一致, 说明外海输入是该区域铵盐的主要来源。另一方面, 氮稳定同位素(δ~(15)N-NO_2~-和δ~(15)N_P)未表现出随盐度的变化规律, 而δ~(18)3O-NO_3~-和δ~(13)C_P 则随盐度升高而增加, 说明淡水输入的同位素值低于海洋水平。通过对比中、高浓度叶绿素水体中NO_3~-、δ~(15)N-NO_3~-、δ~(18)O-NO_3~-的变化特征可以看出, 随NO_3~-浓度降低, δ~(15)N-NO_3~-值升高, 且呈现 6.2‰的分馏系数, 且氧同位素也随之增大, 指示水体中浮游植物对硝酸盐的同化吸收作用。而另一方面, 两种同位素的增加差值表现出△δ~(18)O︰△δ~(15)N1 , 说明硝酸盐在被消耗的同时还发生着补充作用。在较高盐度的水体中, 发现4NH(10)呈现出向硝酸盐的转化趋势并引起δ~(15)N-NO_3~-降低, 指示了底部明显的硝化过程, 与此前的研究结果一致。本文结果以期丰富对河口区氮循环和迁移转化的认知。     

氮限制时间对海绿球藻和微绿球藻生长、总脂含量及脂肪酸组成的影响

本文研究了不同氮限制时间(0、1、2、4、6 d)对海绿球藻(Halochlorococcum sarcotum)和微绿球藻(Nannochloris oculata)叶绿素荧光参数、细胞密度、生物量、叶绿素含量、总脂含量以及脂肪酸组成的影响。本实验结果表明,海绿球藻的最大相对电子传递速率rETR_(max)和快速光曲线的初始斜率α都随氮限制时间增加而降低,而光系统II最大光能转化效率F_v/F_m、非光化学淬灭NPQ以及最小饱和光照强度Ik都有先增加后下降的趋势,各参数都在氮限制第6d达到最小值。微绿球藻上述各参数的变化趋势均为随着氮限制时间增加而逐渐下降。随着氮限制时间增加,海绿球藻和微绿球藻细胞密度都有较小幅度的增加,分别在第5 d和第6 d达到最大值;两种绿藻的叶绿素含量均随氮限制时间的增加而降低,氮限制0 d时叶绿素含量最高, 6 d时叶绿素含量最低;在氮限制第2 d时二者总脂产率都达到最大值,分别为0.021 g·(L·d)~(–1)和0.017 g·(L·d)~(–1),由此可见,适合海绿球藻和微绿球藻产脂的最佳氮限制时间均为2 d。海绿球藻和微绿球藻的脂肪酸主要包括16:0、18:0、20:0、18:1n-9、18:2n-6和16:3n-3等。氮限制对海绿球藻的18:1n-9和MUFA(单不饱和脂肪酸总和)影响显著,均随氮限制时间增加而增加,而PUFA(多不饱和脂肪酸总和)含量随氮限制时间增加而降低;氮限制对微绿球藻的16:0、18:1n-9、16:3n-3、MUFA和PUFA有显著影响,随着氮限制时间增加, 16:0、18:1n-9及MUFA含量逐渐增加,而16:3n-3和PUFA含量逐渐降低。本实验结果可为进一步开发海绿球藻和微绿球藻并对其进行大规模培养提供理论依据。     

全国行业COD和TN污染物产强环境准入基准体系研究

围绕当前中国源头治理与产业转型升级之间脱节严重的突出问题,在编制行业小类污染源全覆盖且取值简便的产强系数等级划分表的基础上,构建全国行业小类农业、工业、服务业和生活源化学耗氧量(COD)和总氮(TN)污染物产强环境准入基准体系,并以青岛市为例,评价污染源产强环境准入基准的可靠性和准确性。通过聚类分组和归并,“全国产强列表手册”编列的3022个COD和1734个TN亚小类污染源归一化产强系数都可划分为13个等级。对于“全国产强列表手册”编列的321个COD和133个TN行业小类,产强准入基准等级构成有显著差异,分别有10和12个等级,其中不同等级占比分别是II-2和IV-6最高,V-9和VI-12最低。根据产强系数检验性监测结果按从严标定准入基准表明,对于青岛市254个COD和109个TN行业小类,产强准入基准构成与全国有所不同,分别有10和11个等级,其中分别有77和14个低于全国准入基准等级。根据青岛市陆源COD和TN产污数量比较分析表明,分级比分类产强核算结果平均相差约6%,远远低于产强系数检验性监测偏差(49%)和13等级产强等级内变幅(39%)。这说明,在按“全国行业小类COD和TN污染物产强环境准入基准体系”建立完善中国污染源产强环境准入制度中,不仅按产污数量分级产强核算结果具有相当的准确性,而且按从严标定准入基准的原则也具有相当的可靠性。     

氮添加降低了半干旱草原土壤呼吸但未改变其温度敏感性

半干旱生态系统土壤呼吸(Rs)对氮添加的响应机制仍有待探索。本研究在中国半干旱草原设置不同氮添加水平(0、2、4、8、16、32 gN m-2 yr-1),测定土壤呼吸速率、土壤温湿度、微生物磷脂脂肪酸、土壤理化性质与地上生物量等指标,探讨氮添加对土壤呼吸及其温度敏感性(Q10)的影响。结果表明:氮添加显著增加了土壤可溶性有机碳(DOC)和无机氮(IN)的含量,降低了土壤pH值,对地上生物量(ABM)无显著影响。氮添加降低了磷脂脂肪酸(PLFAs)的总量,降低了真菌细菌比(F:B),提高了革兰氏阳性阴性菌比(G+:G–)。氮添加显著降低了土壤呼吸,N2、N4、N8、N16和N32处理下的土壤呼吸分别比对照N0变化了–2.58%、14.86%、22.62%、23.97%和19.87%,结构方程模型表明,氮添加通过降低PLFAs总量和改变微生物组成降低土壤呼吸。氮添加对温度敏感性(Q10)、土壤总有机碳(TOC)和总氮(TN)的影响均不显著,表明氮添加减轻了土壤碳的损失,且不会改变全球变暖背景下土壤有机碳矿化的潜力。     

渤海氮污染的来源结构与污染压力空间分布

近30年渤海环境发生了巨大变化,陆源污染输入是导致渤海环境恶化的主要原因。为研究陆源污染压力强度与海域污染的空间关系,采用层级嵌套的水污染输出分区方法,将环渤海地区划分为23个陆海统筹管理分区,并基于土地利用数据、社会经济统计数据和污染普查等资料,估算出环渤海地区五类社会经济活动的总氮排放量,进而分析各分区单元的陆源污染压力。研究结果表明：① 渤海周边陆域总氮排放量约85万t,农业农村面源污染是氮污染的主要来源,占总排放量的57.4%,工业污染贡献有限,渤海湾沿岸城镇居民生活排放突出;② 23个陆海统筹管理分区之间的污染压力差异巨大,辽东湾、渤海湾和莱州湾周边的分区陆源污染压力大,其它分区的压力相对较低,各分区内陆域污染压力与对应海域污染状况在空间上高度一致;③ 各分区之间污染的来源构成差异显著,渤海湾氮污染的主要来源是居民生活排放,辽东湾工业污染相对突出,莱州湾农业面源污染占比大;④ 渤海周边陆源污染排海压力短期内难以缓解。     

楚科奇和西伯利亚陆架颗粒有机物的来源：碳、氮同位素的线索

The stable isotopic composition(δ~(13)C and δ~(15)N) 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. The δ~(13)C_(POC) values were in the range of -29.5‰ to-17.5‰ with an average of -25.9‰±2.0‰, and the δ~(15)N_(PN) 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 the δ~(13)C and δ~(15)N values were just the opposite. Abnormally low C/N ratios(4), low δ~(13)C_(POC)(almost-28‰) and high δ~(15)N_(PN)(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.