临淄地区地下水中氮的水文地球化学行为

临淄地区地下水普遍受到氮的污染其主要形式为ＮＯ３＾－、ＮＯ２＾－和ＮＨ４＾＋三种溶解离子态。这三种离子在包气带及其上部土壤层中产生交换吸附及氧化还原现象。实验表明：该区土壤对ＮＨ４＾＋的吸附净化率９９％以上，且吸附量由层表向下递减；同时有Ｃａ＾２＋等被解吸，导致地下水总硬度增高，其总硬度与Ｃａ＾２＋的历时曲线完全相似；氮在包气带中的氧化还原反应主要表现为一级硝化作用。     

对碘偶氮氯膦与铅显色反应及其应用

研究了对碘偶氮氯膦（ＣＰＡ－ｐＩ）与Ｐｂ￣２＋的显色反应。在ｐＨ５．８的（ＣＨ＿２）＿６Ｎ。－ＮＯ＿３缓冲介质中，Ｐｂ￣２＋与ＣＰＡ－ｐｌ形成１：２的蓝绿色配合物，在６７５ｎｍ处测定配合物的吸光度，其表现摩尔吸光系数为２．４７×１０￣４Ｌ．ｍｏｌ￣－１·ｃｍ￣－１Ｐｂ￣２＋浓度在０～１．１６×１０￣－５ｍｏｌ／Ｌ即０～２．４μｍｌ）符合比尔定律。试验了２０余种共存离子的影响，经共沉淀结合巯基棉分离预处理试样溶液后，测定了硫精砂中微量Ｐｂ的含量。     

中国东部橄榄岩包体和榴辉岩中CO2流体包裹体的碳同位素组成

应用阶段段加热技术,对中国东部新生代玄武岩中的橄榄岩包体和大别造山带超高压榴辉岩进行了裹体ＣＯ２的碳同位素组成测定,结果表明,榄岩的δ＾１３Ｃ值变化较大,从－２２．８％到＋０．７‰到＋４．６‰,同样明显不同于前人报道的低δ＾１３Ｃ值（－３０‰２０～－２０‰）特征,大别造山带榴辉岩的δ＾１３Ｃ变化从－１８．５‰到＋４．６‰,同样明显不同于前人报道的低δ＾１３Ｃ值（－３０‰～－２０‰）特征。榴辉;岩的     

利用氮同位素技术识别石家庄市地下水硝酸盐污染源

地下水NO－ 3污染是石家庄市地下水管理面临的一个主要问题。本次研究通过地下水及其潜在补给源的氮同位素和水化学调查，确定和识别石家庄市地下水NO－ 3污染程度和污染源。地下水中的无机氮化合物主要以NO－ 3形式存在，浓度变化在 2．65～152．1 m g／L之间，均值为（54．88± 31）m g／L（ n＝44），48％的样品浓度超过国际饮水标准（50 m g／L）。地下水样品的NO－ 3－ 15 N值域＋4．53‰～＋25．36‰，均值＋9．94‰±4．40‰（ n＝34）。34个样品中，22个样品（65％）的氮同位素值大于＋8‰；与1991年相比，氮同位素组成指示地下水NO－ 3的主要来源已由当时矿化的土壤有机氮变为现在的动物粪便或污水；结合Cl－分析，南部地下水NO－3还受到东明渠污水的影响。其余12个样品（35％）的氮同位素值变化在＋4‰～＋8‰之间，其中 15 N值较大的（＋6‰～＋8‰）指示来自土壤有机氮，较小的（＋4‰～＋6‰）指示来自氨挥发较弱、快速入渗的化肥厂污水。根据上述研究结果，提出了改善石家庄市地下水管理的措施。     

298K时三元体系K^＋／CO3^2—,B4O7^2——H2O和Li^＋／CO3^2—,B4O7^2——H2O相关系

研究了二个三元体系Ｌｉ＋／ＣＯ２－３,Ｂ４Ｏ２－７Ｈ２Ｏ（１）和Ｋ＋／ＣＯ２－３,Ｂ４Ｏ２－７Ｈ２０（２）２９８Ｋ时的相平衡关系和平衡液相的物化性质（密度、折光密、粘度、电导率、ｐＨ值）。研究表明：这二个三元体系均属简单共饱型,无复盐或固溶体形成。体系（１）的两段溶解度曲线对应于无水Ｌｉ２ＣＯ３和Ｌｉ２Ｂ４Ｏ７·３Ｈ２Ｏ结晶区,体系（２）的两段溶解度曲线对应于Ｋ２ＣＯ３·３／２Ｈ２Ｏ和Ｋ２Ｂ４Ｏ７·４Ｈ２Ｏ结晶区。     

湖南石门雄黄矿床流体包裹体地球化学特征

石门超大型雄黄矿床流体包裹体丰富。包裹体液相成分中富Ｎａ＋、Ｃｌ－和Ｋ＋、ＳＯ２－４，气相成分中Ｈ２Ｏ占绝对优势，少量ＣＯ２，成矿流体化学类型属Ｃｌ ＳＯ４ Ｎａ Ｋ型水。雄黄、雌黄形成于低温（１８０～９０℃）、低压（２０～５ＭＰａ）、浅成（１７５～７００ｍ）、弱酸性（ｐＨ：４．６７、４．４３）和弱还原（Ｅｈ：－０．２６５Ｖ）条件。流体包裹体氢氧同位素研究表明，成矿流体主要为古大气降水，并混有盆地建造水，大气降水下渗、循环、加热、淋滤形成了中－低盐度［ｗ（ＮａＣｌ）：１６．０３％～４．２７％］，中等密度（０．８６３～１．０６５ｇ／ｃｍ３），含矿地下热水。     

邻羟基苯基重氮氨基偶氮苯与铜显色反应的研究及应用

研究了邻羟基苯基重氮氨基偶氮苯与Ｃｕ＾２＋的显色反应。在乳化剂ＯＰ存在下及ＰＨ１０．０－１２．０的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ缓冲介质中，Ｃｕ＾２＋和ｏ－ＨＤＡＡ形成１“３的红色配合物，其最大吸收波长为５４６ｎｍ，表观摩尔吸光系数４．２０＊１０＾４Ｌ．ｍｏｌ＾－３．ｃｍ＾－１。     

meso—四（2—磺酸萘基）卟啉与锰（Ⅱ）显色反应研究

研究了新合成的ｍｅｓｏ－四（２－磺酸萘基）卟啉（ＴＮＰＳ４）与Ｍｎ＾２＋的显色反应。在ｐＨ８．０的Ｎａ２Ｂ４Ｏ７－ＨＣｌ缓冲溶液中，ＴＮＰＳ４与Ｍｎ＾２＋形成稳定的配合物，最大吸收波长４７０ｎｍ，配合物组成为ＴＮＰＳ４：Ｍｎ＾２＋＝２：１，表观摩尔吸光系数ε＝１．０３×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，线性范围０．０－５．０μｇＭｎ＾２＋／２５ｍｌ。用于化探样品中Ｍｎ的测定，结果令人满意。     

催化褪色光度法测定痕量锰的研究及应用

本研究了在ＰＨ＝４．０醋酸－醋酸钠缓冲溶液中，锰催化ＫＩＯ４氧化５－Ｂｒ－ＰＡＤＡＰ的褪色反应及其动力学条件，建立了一个痕量锰的高灵敏度新方法，方法灵敏度为１．３２×１０＾－１０ｇ／ｍｌ，测定范围Ｍｎ＾２＋浓度为０￣１．５μｇ／ｍｌ，用于测定人发，自来水，茶叶中痕量锰，结果满意。     

铜矿峪铜矿床地球化学的研究

详细地研究了铜矿峪矿床地球化学特征，得出铜矿床形成的ｐｂ－ｐｂ年龄为２１亿年；矿床形成温度为３５０℃，压力为４×１０￣７ｐａ～１×１０￣８ｐａ；Ｌｏｇｆｏ＿２：为－３１～－３１．８８，ｌｏｇｆｓ＿２为－５～－８；ｐＨ值为３．６～６．４；硫化物的δ￣３４Ｓ值为－４．５‰～０．２‰，δ￣３４Ｓ为＋１０‰；方解石的δ￣１３Ｃ为－４．８９‰～１．１‰，δ￣１３Ｃ为一４．２８‰，成矿流体主要为岩浆水，属于斑岩型铜矿床。     

利用樟树叶片氮含量和同位素组成初探武汉市大气氮沉降和氮源

为了解武汉市不同城市功能区大气氮沉降的具体特征,对城市交通区、工业区、文教区和市郊交通区、文教区5个功能区的樟树叶片及根际土壤的氮含量和氮同位素组成进行测定,发现城市公路、工厂附近和大学校园的樟树叶片的氮含量明显高于市郊大学校园和公路.城市公路、工厂附近的樟树叶片的氮同位素分别受控于汽车尾气排放的氮氧化物(NOx)、工...     

硝酸盐氮氧稳定同位素分馏过程记录的海洋氮循环研究进展

海洋生态系统中的氮素生物地球化学循环主要是由微生物的代谢过程来驱动的,包括氮固定、氮同化、硝化以及反硝化和厌氧氨氧化过程,这些过程都伴随着不同程度的氮氧同位素的分馏,直接影响着海洋硝酸盐中的氮氧稳定同位素组成.因此,通过检测海洋硝酸盐中的氮氧稳定同位素信号,就可以捕捉到海洋中发生的具体氮素循环过程.细菌反硝化法是这一研究最有力的手段,通过细菌的作用把硝酸盐中记录的氮氧稳定同位素信号转化到N2O中,再通过痕量N2O的同位素质谱测定和分析,准确地反映海洋中发生的氮素转化过程.硝酸盐氮氧稳定同位素分馏过程为深入理解海洋氮循环提供了一个重要的工具,有力推动了海洋氮素生物地球化学的研究,在近10年来取得了重要进展.     

Nitrogen Stable Isotopes of Macrophytes Assess Stormwater Nitrogen Inputs to an Urbanized Estuary

The ¹⁵N composition of seagrass and benthic macroalgae from shallow waters of Sarasota Bay was measured to determine if stable N isotopes can be used to trace stormwater N into macrophyte production within an urbanized estuary. Results show isotopically enriched macroalgae at the landward stations near creeks and bayous in the central Bay and in the southern portion of the Bay. A known sewage outfall at Whitaker Bayou resulted in δ ¹⁵NO₃ values from 0 to +9‰. Isotopically enriched NH₄ values in Phillippi Creek (+10 to +17‰) were similar to the stormwater ¹⁵NH₄ values from the watershed (+7 to +18‰). Enriched N sources supported a significant portion of macroalgae N demands in the southern reaches of the Bay while isotopically depleted N sources (i.e., atmospheric deposition and/or fertilizers) appear to be more important for macroalgae in the northern portion of the Bay. Macroalgae were typically more enriched than seagrass and appear to be better indicators of anthropogenic loadings near creeks and bayous that receive large volumes of stormwater and other anthropogenic N sources. Historically, studies have used enriched ¹⁵N in macrophytes to infer wastewater influences. This study shows that stormwater N inputs need to be considered in nitrogen budgets for aquatic systems that show anthropogenic ¹⁵N enrichment.     

离子交换色层法测定低浓度铵态氮水样的氮同位素研究

采用氯化铵、氯化钾为原料的离子交换色层法结合扩散法处理低浓度铵态氮水样,测定其铵态氮同位素时,减小全流程空白、避免同位素分馏、获取准确的铵态氮同位素值是需解决的关键问题.本文建立一套尽可能密闭的离子交换系统,避免了在大气环境下低浓度铵态氮水样在离子交换色层预处理过程中的污染;采用蠕动泵过柱的方法,调节蠕动泵的转速控制氯化铵溶液的过柱速率为1.2 L/h,洗脱速率为0.2 L/h,缩短了样品处理时间,减少了空气对铵态氮样品的污染,样品中的NH4+可完全被阳离子交换树脂吸附,铵态氮回收率为93.5％ ～102.8％,且不会引起氮同位素分馏;将优级纯氯化钾试剂置于450℃马弗炉中灼烧24 h,降低了氯化钾试剂引入的铵态氮污染.建立的方法使全流程的铵态氮空白浓度低于检出限0.02 mg/L,解决了在大气环境下采用离子交换色层法处理低浓度铵态氮水样的污染问题,加速了样品前处理的过程,提高了样品处理效率.     

Nitrogen in Chinese coals

Three hundred and six coal samples were taken from main coal mines of twenty-six provinces,autonomous regions,and municipalities in China,according to the resource distribution and coal-forming periods as well as the coal ranks and coal yields.Nitrogen was determined by using the Kjeldahl method at U.S.Geological Survey(USGS),which exhibit a normal frequency distribution.The nitrogen contents of over 90% Chinese coal vary from 0.52% to 1.41% and the average nitrogen content is recommended to be 0.98%.Nitrogen in coal exists primarily in organic form.There is a slight positive relationship between nitrogen content and coal ranking.     

Nitrogen in Chinese coals

Three hundred and six coal samples were taken from the main coal mines of twenty-six provinces, autonomous regions, and municipalities of China. The method of Kjeldahl-Gunning Analysis was used to measure the nitrogen contents in the samples. Nitrogen in coals is principally of organic nature. A weak positive correlation between coal rank and nitrogen content is inferred in the study. The distribution of nitrogen in each geological age, coal-cumulating area and province＇s coals was studied. The contents of nitrogen in Chinese coals show approximately a normal distribution, and 90% of the values range from 0.52% to 1.41%, the average nitrogen content in Chinese coals is designated as the arithmetic mean, 0.98%.     

Nitrogen in chondritic metal

We report new nitrogen isotopic data in metals of H-, L- and one LL -chondrites, with N abundances in the range of ∼0.3 to 3.3 ppm and half of these <1 ppm. Nitrogen isotopic signatures in metals with low indigenous N concentrations are modified by cosmic ray spallation components; corrections are required to determine the indigenous N signatures. The metals of type 4 and 5 show uniform indigenous nitrogen (δ¹⁵N = −6.8 ± 0.5 ‰) and confirm a reported possible genetic association of chondritic metal with metal in IIE and IVA iron meteorites. Distinct isotopic signatures are observed in two metal samples of the Portales Valley (H6) meteorite which both are inconsistent with signatures in H4 and H5 chondrites, but possibly reveal a record of impact-induced melting and metamorphism on the parent asteroid. Anomalous nitrogen signatures in metals of type 3 chondrites, on the other hand, may reflect residues of surviving presolar isotopic signatures.     

Nitrogen components in ureilites

Abundances and isotopic compositions of nitrogen and argon have been investigated in bulk samples as well as in acid-resistant C-rich residues of a suite of ureilites consisting of six monomict (Haverö, Kenna, Lahrauli, ALH81101, ALH82130, LEW85328), three polymict (Nilpena, EET87720, EET83309), and the diamond-free ureilite ALH78019. Nitrogen in bulk ureilites varies from 6.3 ppm (in ALH 78019) to ∼55 ppm (in ALH82130), whereas C-rich acid residues have ∼65 to ∼530 ppm N, showing approximately an order of magnitude enrichment, compared with the bulk ureilites, somewhat less than trapped noble gases. Unlike trapped noble gases that show uniform isotopic composition, nitrogen shows a wide variation in δ¹⁵N values within a given ureilite as well as among different ureilites. The variations observed in δ¹⁵N among the ureilites studied here suggest the presence of at least five nitrogen components. The characteristics of these five N components and their carrier phases have been identified through their release temperature during pyrolysis and combustion, their association with trapped noble gases, and their carbon (monitored as CO + CO₂ generated during combustion). Carrier phases are as follows: 1) Amorphous C, as found in diamond-free ureilite ALH78019, combusting at ≤500°C, with δ¹⁵N = -21‰ and accompanied by trapped noble gases. Amorphous C in all diamond-bearing ureilites has evolved from this primary component through almost complete loss of noble gases, but only partial N loss, leading to variable enrichments in ¹⁵N. 2) Amorphous C as found in EET83309, with similar release characteristics as component 1, δ¹⁵N ≥ 50‰ and associated with trapped noble gases. 3) Graphite, as clearly seen in ALH78019, combusting at ≥700°C, δ¹⁵N ≥ 19‰ and devoid of noble gases. 4) Diamond, combusting at 600-800°C, δ¹⁵N ≤ -100‰ and accompanied by trapped noble gases. 5) Acid-soluble phases (silicates and metal) as inferred from mass balance are expected to contain a large proportion of nitrogen (18 to 75%) with δ¹⁵N in the range -25‰ to 600‰. Each of the ureilites contains at least three N components carried by acid-resistant C phases (amorphous C of type 1 or 2, graphite, and diamond) and one acid-soluble phase in different proportions, resulting in the observed heterogeneity in δ¹⁵N. In addition to these five widespread components, EET83309 needs an additional sixth N component carried by a C phase, combusting at <700°C, with δ¹⁵N ≥ 153‰ and accompanied by noble gases. It could be either noble gas-bearing graphite or more likely cohenite. Some excursions in the δ¹⁵N release patterns of polymict ureilites are suggestive of contributions from foreign clasts that might be present in them.Nitrogen isotopic systematics of EET83309 clearly confirm the absence of diamond in this polymict ureilite, whereas the presence of diamond is clearly indicated for ALH82130. Amorphous C in ALH78019 exhibits close similarities to phase Q of chondrites.The uniform δ¹⁵N value of −113 ± 13 ‰ for diamond from both monomict and polymict ureilites and its independence from bulk ureilite δ¹⁵N, Δ¹⁷O, and %Fo clearly suggest that the occurrence of diamond in ureilites is not a consequence of parent body-related process. The large differences between the δ¹⁵N of diamond and other C phases among ureilites do not favor in situ shock conversion of graphite or amorphous C into diamond. A nebular origin for diamond as well as the other C phases is most favored by these data. Also the preservation of the nitrogen isotopic heterogeneity among the carbon phases and the silicates will be more consistent with ureilite formation models akin to “nebular sedimentation” than to “magmatic” type.     

气相分子吸收光谱法测定土壤中铵态氮和硝态氮的含量

通过测定土壤中铵态氮和硝态氮的含量,能够为农业领域土壤精准施肥和土壤的环境保护提供重要参考。目前基于分光光度法的土壤中铵态氮和硝态氮的分析方法容易受到提取试液颜色、浑浊度、其他共存离子等干扰不能直接测定,必须进行脱色等前处理操作,费时耗力。因此,本文建立了一次性同时浸提,不经脱色处理,采用气相分子吸收光谱法测定农田土壤中铵态氮和硝态氮含量的方法。利用该方法测定农田土壤中铵态氮和硝态氮,避免了繁琐的显色反应过程,一个批次样品(50个)的分析流程仅需5h。在0.10~2.00mg/L(铵态氮)和0.20~4.00mg/L(硝态氮)浓度范围内,工作曲线线性良好;方法检出限分别为0.013mg/kg及0.002mg/kg;相对标准偏差(RSD)<1%;加标回收率为96.3%~100.7%。较之基于传统分光光度法的国家标准方法,本方法在检出限、精密度和回收率等指标方面均有显著改善,能够满足农田土壤中铵态氮和硝态氮的批量精准分析需求。     

Atmospheric Reactive Nitrogen Cycle and Stable Nitrogen Isotope Processes: Progresses and Perspectives

Oxidized reactive nitrogen in the atmosphere mainly consists of nitrogen oxides (NO _X =NO+NO₂, NO₃) and nitric acid. The atmospheric cycling of NO _X influences the formation of ozone and hydroxyl radicals that are important for atmospheric oxidation capacity. Nitric acid, the final product of NO _X oxidation, not only is an important component of particulate pollutants, but also has a direct impact on the ecosystem through dry and wet deposition. The stable nitrogen isotope (δ¹⁵N) shows the potential to study reactive nitrogen cycle, and to trace the emission, transport and deposition of reactive nitrogen from local to global scales. Here, we reviewed previous studies using δ¹⁵N to investigate NO _X emission and atmospheric reactive nitrogen cycle, and discuss the uncertainties of δ¹⁵N signatures of different NO _X sources from two aspects: NO _X generation mechanism and NO _X collection methods. We also discussed the nitrogen isotope fractionation and the consequences during the conversions of NO _y molecules. We ended up with discussions on the possibility of using δ¹⁵N to trace NO _X emissions. Although there are still large uncertainties in quantifying and tracing NO _X emissions using nitrogen stable isotopes, such isotope tool is efficient enough to trace reactive nitrogen cycles in the atmosphere. On the basis of this, we proposed that we can combine atmospheric chemistry transmission models with isotope tracers to improve our understanding of regional and global atmospheric reactive nitrogen cycle regarding the fluxes of different emission sources, their atmospheric transformation, etc.