Hua-Yun Xiao

Atmospheric transport of urban-derived NHx: Evidence from nitrogen concentration and δ15N in epilithic mosses at Guiyang, SW China

Nitrogen concentration and delta15N in 175 epilithic moss samples were investigated along four directions from urban to rural sites in Guiyang, SW China. The spatial variations of moss N concentration and delta15N revealed that atmospheric N deposition is dominated by NHx-N from two major sources (urban sewage NH3 and agricultural NH3), the deposition of urban-derived NHx followed a point source pattern characterized by an exponential decline with distance from the urban center, while the agricultural-derived NHx was shown to be a non-point source. The relationship between moss N concentration and distance (y=1.5e(-0.13x)+1.26) indicated that the maximum transporting distance of urban-derived NHx averaged 41 km from the urban center, and it could be determined from the relationship between moss delta(15)N and distance [y=2.54ln(x)-12.227] that urban-derived NHx was proportionally lower than agricultural-derived NHx in N deposition at sites beyond 17.2 km from the urban center. Consequently, the variation of urban-derived NHx with distance from the urban center could be modeled as y=56.272e(-0.116x)-0.481 in the Guiyang area.

Nitrogen isotope variations in camphor (Cinnamomum Camphora) leaves of different ages in upper and lower canopies as an indicator of atmospheric nitrogen sources

Nitrogen isotopic composition of new, middle-aged and old camphor leaves in upper and lower canopies has been determined in a living area, near a motorway and near an industrial area (Jiangan Chemical Fertilizer Plant). We found that at sites near roads, more positive δ(15)N values were observed in the camphor leaves, especially in old leaves of upper canopies, and ∆δ(15)N=δ(15)N(upper)-δ(15)N(lower)>0, while those near the industrial area had more negative δ(15)N values and ∆δ(15)N<0. These could be explained by two isotopically different atmospheric N sources: greater uptake from isotopically heavy pools of atmospheric NO(x) by old leaves in upper canopies at sites adjacent to roads, and greater uptake of (15)N-depleted NH(y) in atmospheric deposition by leaves at sites near the industrial area. This study presents novel evidence that (15)N natural abundance of camphor leaves can be used as a robust indicator of atmospheric N sources.

Response of stable carbon isotope in epilithic mosses to atmospheric nitrogen deposition.

Epilithic mosses are characterized by insulation from substratum N and hence meet their N demand only by deposited N. This study investigated tissue C, total Chl and delta13C of epilithic mosses along 2 transects across Guiyang urban (SW China), aiming at testing their responses to N deposition. Tissue C and total Chl decreased from the urban to rural, but delta13C(moss) became less negative. With measurements of atmospheric CO2 and delta13CO2, elevated N deposition was inferred as a primary factor for changes in moss C and isotopic signatures. Correlations between total Chl, tissue C and N signals indicated a nutritional effect on C fixation of epilithic mosses, but the response of delta13C(moss) to N deposition could not be clearly differentiated from effects of other factors. Collective evidences suggest that C signals of epilithic mosses are useful proxies for N deposition but further works on physiological mechanisms are still needed.

Tissue S/N ratios and stable isotopes (δ34S and δ15N) of epilithic mosses (Haplocladium microphyllum) for showing air pollution in urban cities in Southern China

In urban cities in Southern China, the tissue S/N ratios of epilithic mosses (Haplocladium microphyllum), varied widely from 0.11 to 0.19, are strongly related to some atmospheric chemical parameters (e.g. rainwater SO(4)(2-)/NH(4)(+) ratios, each people SO(2) emission). If tissue S/N ratios in the healthy moss species tend to maintain a constant ratio of 0.15 in unpolluted area, our study cities can be divided into two classes: class I (S/N > 0.15, S excess) and class II (S/N < 0.15, N excess), possibly indicative of stronger industrial activity and higher density of population, respectively. Mosses in all these cities obtained S and N from rainwater at a similar ratio. Sulphur and N isotope ratios in mosses are found significantly linearly correlated with local coal delta(34)S and NH(4)(+)-N wet deposition, respectively, indicating that local coal and animal NH(3) are the major atmospheric S and N sources.

Assessment of atmospheric sulfur with the epilithic moss Haplocladium microphyllum: Evidences from tissue sulfur and δ34S analysis

The application of geochemical signals in mosses is more and more popular to investigate the deposition of atmospheric pollutants, but it is unclear whether records of atmospheric sulfur in mosses differ between their diverse habitats. This study aimed to investigate the influence of growing condition on tissue sulfur and delta34S of Haplocladium microphyllum. Epilithic and terricolous mosses in open fields, mosses under different canopy conditions were considered. We found that tissue sulfur and delta34S of mosses under different habitats were not consistent and could not be compared for atmospheric sulfur research with each other even collected at the same site, moss sulfur and delta34S records would be distorted by subsoil and upper canopies in different degrees, which possibly mislead the interpretation of atmospheric sulfur level and sources. Consequently, mosses on open rocks can be used reliably to assess atmospheric-derived sulfur in view of their identical sulfur and delta34S evidences.

Sulfur isotopic signatures in rainwater and moss Haplocladium microphyllum indicating atmospheric sulfur sources in Nanchang City (SE China)

Sulfur source identification previously reported has been based on sulfur isotopic ratios in either rainwater or mosses. The δ(34)S values of rainwater sulfate and the epilithic moss Haplocladium microphyllum in Nanchang region (China) were determined for comparisons and used to delineate atmospheric sulfur sources. At the urban and rural sites, similar mean δ(34)S values were observed between rainwater sulfate (+1.6‰ and -0.2‰, respectively) and epilithic mosses (+1.7‰ and +0.6‰, respectively), suggesting that mosses acquire δ(34)S values similar to those found for rainwater sulfate. This has further demonstrated that moss δ(34)S signatures hold valuable source-specific information as rainwater δ(34)S values do. The δ(34)S values of both rainwater sulfate and epilithic mosses indicated that atmospheric sulfur in Nanchang region was mainly associated with coal combustion. The lower δ(34)S values at the rural site can be explained by higher contribution of local coals (lower δ(34)S values relative to those of north Chinese coals) and biogenic sulfur.

Indicating atmospheric sulfur by means of S-isotope in leaves of the plane, osmanthus and camphor trees.

Foliar δ(34)S values of three soil-growing plant species (Platanus Orientalis L., Osmanthus fragrans L. and Cinnamomum camphora) have been analyzed to indicate atmospheric sulfur. The foliar δ(34)S values of the three plant species averaged -3.11±1.94‰, similar to those of both soil sulfur (-3.73±1.04‰) and rainwater sulfate (-3.07±2.74‰). This may indicate that little isotopic fractionation had taken place in the process of sulfur uptake by root or leaves. The δ(34)S values changed little in the transition from mature leaves to old/senescing leaves for both the plane tree and the osmanthus tree, suggestive of little isotope effect during sulfur redistribution in plant tissues. Significantly linear correlation between δ(34)S values of leaves and rainwater sulfate for the plane and osmanthus trees allowed the tracing of temporal variations of atmospheric sulfur by means of foliar sulfur isotope, while foliage δ(34)S values of the camphor is not an effective indicator of atmospheric sulfur.

Distribution of Selenium in Corn and Its Relationship With Soil Selenium in Yutangba Mini-Landscape *

Within the range of 0.01 km mini-landscape in Yutangba, Enshi, Hubei Province, the content of Se in corn is very high. The average Se contents in root, stem, leaf and seed of corn were estimated to be 4.36±3. 27mg/kg, 3.08±2.24 mg/kg, 9.74±7.62mg/kg, and 8.07±5.02mg/kg, respectively. The research results show that there is a significantly positive correlation between corn selenium and soil selenium, and thus according to the distribution of Se in corn, three subregions can be divided in Yutangba. The content of selenium in corn is controlled by that of soil. A little variation in selenium content in soil will lead to a considerable corresponding variation in corn. So it is deduced that the organs that contain relatively high Se in plants may be used as a sensitive selenium indicator of Se levels in the environment.Within the range of 0.01 km mini-landscape in Yutangba, Enshi, Hubei Province, the content of Se in corn is very high. The average Se contents in root, stem, leaf and seed of corn were estimated to be 4.36±3. 27mg/kg, 3.08±2.24 mg/kg, 9.74±7.62mg/kg, and 8.07±5.02mg/kg, respectively. The research results show that there is a significantly positive correlation between corn selenium and soil selenium, and thus according to the distribution of Se in corn, three subregions can be divided in Yutangba. The content of selenium in corn is controlled by that of soil. A little variation in selenium content in soil will lead to a considerable corresponding variation in corn. So it is deduced that the organs that contain relatively high Se in plants may be used as a sensitive selenium indicator of Se levels in the environment.

A reliable compound-specific nitrogen isotope analysis of amino acids by GC-C-IRMS following derivatisation into N-pivaloyl-iso-propyl (NPIP)esters for high-resolution food webs estimation.

The signatures of natural stable nitrogen isotopic composition (δ(15)N) of individual amino acid (AA) have been confirmed to be a potentially effective tool for elucidating nitrogen cycling and trophic position of various organisms in food webs. In the present study, a two-stage derivatisation approach of esterification followed by acylation was evaluated. The biological samples underwent acid hydrolysis and the released individual AA was derivatived into corresponding N-pivaloyl-isopropyl (NPIP) esters for nitrogen isotopic analysis in gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Usually, 13 individual AA derivatives were separated with fine baseline resolution based on a nonpolar gas chromatography column (DB-5ms). The minimum sample amount required under the presented conditions is larger than 20ngN on column in order to accurately determine the δ(15)N values. The δ(15)N values determined by GC-C-IRMS with a precision of better than 1‰, were within 1‰ after empirical correction compared to the corresponding measured by element analysis (EA)-IRMS. Bland-Altman plot showed highly consistency of the δ(15)N values determined by the two measurement techniques. Cation-exchange chromatography was applied to remove interfering fraction from the extracts of plant and animal samples and without nitrogen isotope fractionation during the treatment procedure. Moreover, this approach was carried out to estimate the trophic level of various natural organisms in a natural lake environment. Results highly proved that the trophic level estimated via the presented AA method well reflected the actual food web structure in natural environments.

Rare-Earth Element Geochemistry of Eclogites from the Ultra-High Pressure Metamorphic Belt in Central China *

Based on their REE contents and REE patterns, eclogites from the ultra-high pressure metamorphic belt in central China may be roughly divided into six types including LREE-rich, LREE-rich + positive Eu anomaly, LREE-rich + negative Eu anomaly, REE patternsmooth, MREE-rich and HREE-rich. The LREE-rich, LREE-rich + positive Eu anomaly and LREE-rich + negative Eu anomaly types of eclogites are dominant. REE types of eclogites in different areas can be compared and the REE features of the same REE type of eclogites in different areas are similar. The results of reconstruction of the primary rocks show that the primary rocks of eclogites possibly are dominated by continental tholeiites which are the product of partial melting of relatively fertile mantle and the rocks of tholeiite crystallization-differentiation. There is perfect evolution relationship among the primary rocks of the LREE-rich, LREE-rich + positive Eu anomaly and LREE-rich + negative Eu anomaly types of eclogites and among those of the REE pattern smooth and MREE-rich types of eclogites, the former three types were derived from continental settings and the latter two from nearly oceanic settings. Meanwhile, it is concluded that the mantle sources of primary rocks of the eclogites are inhomogeneous and the primary rocks of eclogites in this area appear to have undergone varying degree of crustal contamination.