•Age-related free amino acid (FAA) δ15N variations in needles were first reported.•FAAs in needles are sensitive biomarkers for atmospheric N pollution.•FAA δ15N variations in needles reflect the main N sources.Free amino acid δ15N values and concentrations of current-year new (new), current-year mature (middle-age) and previous-year (old) Pinus massoniana (Lamb.) needles were determined for five sites with different distances from a highway in a forest in Guiyang (SW China). Needle free amino acid concentrations decreased with increasing distance from the highway, and only the free amino acid concentrations (total free amino acid, arginine, γ-aminobutyric acid, valine, alanine and proline) in the middle-aged needles demonstrated a strong correlation with distance from the highway, indicating that free amino acid concentrations in middle-aged needles may be a more suitable indicator of nitrogen (N) deposition compared to new and old needles. Needle free amino acid δ15N values were more positive near the highway compared to the more distant sites and increased with increasing needle age, indicating that N deposition in this site may be dominated by isotopically heavy NOx-N from traffic emissions. In sites beyond 400 m from the highway, the δ15N values of total free amino acids, histidine, glutamine, proline, alanine, aspartate, isoleucine, lysine, arginine and serine in each age of needle were noticeably negative compared to their respective δ15N values near the highway. This suggested that needle free amino acid δ15N values from these sites were more affected by 15N-depleted atmospheric NHx-N from soil emissions. This result was further supported by the similarity in the negative moss δ15N values at these sites to the δ15N values of soil-derived NHx-N. Needle free amino acid δ15N values therefore have the potential to provide information about atmospheric N sources. We conclude that needle free amino acid concentrations are sensitive indicators of N deposition and that the age-related free amino acid δ15N values in needles can efficiently reflect atmospheric N sources. This would probably promote the application of the combined plant tissue amino acid concentration and δ15N analyses in N deposition bio-monitoring.

•Concentrations and δ15N signatures of NO3−, NH4+ and DON in urban precipitation were measured at Guiyang, SW China.•Major sources of precipitation NH4+ and NO3− were estimated by a Bayesian isotope mixing model (SIAR).•Non-fossil-derived NOx and fossil-derived NH3 are important contributors of inorganic N in urban precipitation.To constrain sources of anthropogenic nitrogen (N) deposition is critical for effective reduction of reactive N emissions and better evaluation of N deposition effects. This study measured δ15N signatures of nitrate (NO3−), ammonium (NH4+) and total dissolved N (TDN) in precipitation at Guiyang, southwestern China and estimated contributions of dominant N sources using a Bayesian isotope mixing model. For NO3−, the contribution of non-fossil N oxides (NOx, mainly from biomass burning (24 ± 12%) and microbial N cycle (26 ± 5%)) equals that of fossil NOx, to which vehicle exhausts (31 ± 19%) contributed more than coal combustion (19 ± 9%). For NH4+, ammonia (NH3) from volatilization sources (mainly animal wastes (22 ± 12%) and fertilizers (22 ± 10%)) contributed less than NH3 from combustion sources (mainly biomass burning (17 ± 8%), vehicle exhausts (19 ± 11%) and coal combustions (19 ± 12%)). Dissolved organic N (DON) accounted for 41% in precipitation TDN deposition during the study period. Precipitation DON had higher δ15N values in cooler months (13.1‰) than in warmer months (−7.0‰), indicating the dominance of primary and secondary ON sources, respectively. These results newly underscored the importance of non-fossil NOx, fossil NH3 and organic N in precipitation N inputs of urban environments.Non-fossil-derived NOx and fossil-derived NH3 are important contributors to precipitation N in urban environments.Download high-res image (228KB)Download full-size image

Spatial interpolation methods have been applied in many environmental research studies. However, it is still a controversial issue to select an appropriate interpolation method for the conversion of discrete sampling sites into continuous maps. This study aimed at selecting an optimal interpolation method to analyze the spatial pattern of atmospheric N deposition in South China. N deposition was calculated by 259 moss sample data. Four spatial interpolation methods, including inverse distance weighting (IDW), radial basis function (RBF), ordinary kriging (OK), and universal kriging (UK), were utilized for modeling the spatial distribution of N deposition. It is the first time that these methods were applied to analyze N deposition in South China. Validation method was used to evaluate the interpolation precision of the various methods, and the cross-validation method was used to evaluate their interpolation accuracy. Comparison of predicted values with measured values indicated that OK was the optimal method for analyzing the spatial distribution of N deposition in this study; it had the highest precision (mean error (ME) = −0.059, root-mean-square error (RMSE) = 5.240, mean relative error (MRE) = 0.129, mean absolute error (MAE) = 4.007) and the lowest uncertainties (standard deviation (SD) = 5.47, coefficient of variation (CV) = 0.15). RBF produced similar results as good as OK, while the worst performed interpolation method was UK. By using the OK method for analyzing N deposition, this work revealed systematic temporal and spatial variations in atmospheric N deposition in South China.

Coal combustion is an important atmospheric pollution source in most Chinese cities, so systematic studies on sulfur and nitrogen in Chinese coals are needed. The sulfur contents in Chinese coals average 0.9 ± 1.0%, indicating that most Chinese coals are low in sulfur. A nearly constant mean δ34S value is observed in low sulfur (TS < 1) Chinese coals of different ages (D, P1, T3 and J3). High sulfur Chinese coals (OS > 0.8%), often found at late Carboniferous (C3) and late Permian (P2) in southern China, had two main sulfur sources (original plant sulfur and secondary sulfur). The wide variety of δ34S values of Chinese coals (−15‰ to +50‰) is a result of a complex sulfur origin. The δ15N values of Chinese coals ranged from −6‰ to +4‰, showing a lack of correlation with coal ages, whereas nitrogen contents are higher in Paleozoic coals than in Mesozoic coals. This may be related to their original precursor plant species: high nitrogen pteridophytes for the Paleozoic coals and low nitrogen gymnosperms for the Mesozoic coals. Different to δ34S values, Chinese coals showed higher δ15N values in marine environments than in freshwater environments.

Tissue N contents and δ15N signatures in 175 epilithic mosses were investigated from urban to rural sites in Guiyang (SW China) to determine atmospheric N deposition. Moss N contents (0.85–2.97%) showed a significant decrease from the urban area (mean = 2.24 ± 0.32%, 0–5 km) to the rural area (mean = 1.27 ± 0.13%, 20–25 km), indicating that the level of N deposition decreased away from the urban environment, while slightly higher N contents re-occurred at sites beyond 30 km, suggesting higher N deposition in more remote rural areas. Moss δ15N ranged from −12.50‰ to −1.39‰ and showed a clear bimodal distribution (−12‰ to −6‰ and −5‰ to −2‰), suggesting that there are two main sources for N deposition in the Guiyang area. More negative δ15N (mean = −8.87 ± 1.65‰) of urban mosses mainly indicated NH3 released from excretory wastes and sewage, while the less negative δ15N (from −3.83 ± 0.82‰ to −2.48 ± 0.95‰) of rural mosses were mainly influenced by agricultural NH3. With more negative values in the urban area than in the rural area, the pattern of moss δ15N variation in Guiyang was found to be opposite to cities where N deposition is dominated by NOx–N. Therefore, NHx–N is the dominant N form deposited in the Guiyang area, which is supported by higher NHx–N than NOx–N in local atmospheric deposition. From the data showing that moss is responding to NHx–N/NOx–N in deposition it can be further demonstrated that the variation of moss δ15N from the Guiyang urban to rural area was more likely controlled by the ratio of urban-NHx/agriculture-NHx than the ratio of NHx–N/NOx–N. The results of this study have extended knowledge of atmospheric N sources in city areas, showing that urban sewage discharge could be important in cities co-generic to Guiyang.

•N concentrations in camphor and Masson pine leaves can indicate N deposition.•δ15N of vascular plant leaves can provide an indication of the main N sources.•15N-enriched traffic NOx-N was the dominant atmospheric N source in urban areas.•15N-depleted agricultural NHx-N was the main atmospheric N source in rural areas.Nitrogen (N) concentrations and δ15N signatures in soil and camphor (Cinnamomum Camphora) and Masson pine (Pinus massoniana Lamb.) leaves collected along an urban-rural gradient in Guiyang (SW China) were investigated systematically. N concentrations in camphor (1.01–2.37%) and Masson pine (0.99–2.42%) leaves showed a significant decrease from central Guiyang (0–6 km) to suburban areas (18–24 km), while slightly increased leaf N concentrations reemerged at areas more than 24 km from the city center. The δ15N values in camphor and Masson pine leaves also decreased from central Guiyang to the rural area, with more positive leaf δ15N in the urban area and 15N-depleted leaf δ15N in the rural area. No significant differences were observed for soil N concentrations and soil δ15N in these areas, which suggested that the decrease in leaf N concentrations was due to decreased atmospheric N deposition along the urban-rural gradient and that there were two isotopically different atmospheric N sources in Guiyang city: foliar δ15N values in urban areas were mainly influenced by 15N-enriched atmospheric NOx-N from traffic emissions, while those in rural areas were primarily affected by 15N-depleted atmospheric NHx-N from agricultural activities. However, the pattern of moss (collected ten years prior, with lower traffic density and wastewater treatment rate in the urban area) δ15N variation in the urban area (0–12 km) was contrary to that of the camphor and Masson pine leaves, indicating that the δ15N values in previously collected urban mosses were mainly controlled by isotopically light NHx-N from untreated wastes and sewage, but were much less affected by traffic. For the trees in the urban area, N concentrations in camphor and Masson pine leaves varied in parallel with their δ15N values (P < 0.0001), and we thus applied a mass balance equation to estimate the δ15N value (about 7‰) in the atmospheric N deposition in the urban area. This indicated that the greater δ15N in urban camphor and Masson pine leaves reflected a higher contribution of NOx-N to N deposition. This study shows that the analysis of N and δ15N in camphor and Masson pine leaves is a promising method to indicate N deposition.

•Free amino acids (FAAs) are sensitive bio-indicators of atmospheric N deposition.•FAAs in young needles are more sensitive to N deposition compared to old needles.•Age-dependent needle δ15N values can be used to identify atmospheric N sources.Free amino acid concentrations and nitrogen (N) isotopic composition in new current-year (new), mature current-year (middle-aged) and previous-year (old) Masson pine (Pinus massoniana Lamb.) needles were determined to indicate atmospheric N deposition in Guiyang (SW China). In different areas, free amino acids (especially arginine) concentrations in new and middle-aged needles were higher than in old needles, and the variation of free amino acids (especially arginine) concentrations in new and middle-aged needles was also greater than in old needles. This indicate that free amino acids in new and middle-aged needles may be more sensitive to N deposition compared to old needles. Moreover, concentrations of total free amino acids, arginine, histidine, γ-aminobutyric acid and alanine in middle-aged needles exhibited a strong relationship with N deposition (P < 0.05). Needle δ15N values showed a strong gradient from central Guiyang to the rural area, with more positive δ15N (especially in old needles) in the city center (0–5 km) and more negative δ15N (especially in old needles) in rural area (30–35 km). These suggest that N deposition in the urban center may be dominated by 15N-enriched NOx-N from traffic exhausts, while it is dominated by isotopically light atmospheric NHx-N from agriculture in rural area. Soil δ15N decreased slightly with distance from the city center, and the difference in δ15N values between the soil and needles (especially for old needles) increased significantly with the distance gradient, indicating that atmospheric N deposition may be an important N source for needles. This study provides novel evidence that free amino acids in needles and age-dependent needle δ15N values are useful indicators of atmospheric N deposition.Download high-res image (114KB)Download full-size image

The analysis of stable isotopes of sulfur (δ34S) is a useful tool for identifying sources of sulfur in soils. Concentrations and sulfur (S) isotopes of water-soluble sulfate (WSS), adsorbed sulfate (AS), residual sulfur (RS), and total sulfur (TS) in uncultivated surface soils of four Chinese provinces were systematically analyzed for identifying sources of S in the soils. Green and healthy mosses (Haplocladium microphyllum) were sampled as bioindicators. The mean WSS concentration (27.8 ± 23.4 mg kg−1) in the surface soils was lower than those of AS (101.4 ± 57.0 mg kg−1) and RS (381.5 ± 256.7 mg kg−1). The mean δ34S values of WSS and AS were very similar (about 2.0%), lower than those of RS (8.0%) and TS (6.1%). A significant linear correlation was found between the δ34S values of AS and WWS (y = 1.0002x – 0.0557, P < 0.0001), indicating that sulfate adsorption in the soils did not markedly fractionate S. All S species in the soils of Guizhou Province were characterized by the lowest δ34S values, consistent with the most 34S-depleted rainwater sulfate reported at Guiyang of Guizhou Province. The δ34S values of sulfate in mosses and rainwater previously reported were significantly linearly correlated with those of both WWS and AS in surface soils, suggesting that atmospheric S input was an important source for soil WSS and AS. However, there were no significant correlations between isotopic composition of rainwater sulfate and RS or TS. The slopes of all these significant linear correlations (soil/rainwater or soil/moss isotopic ratio) were 0.4–0.6, indicating that inorganic sulfate in the surface soils should be a result of mixing of deposited atmospheric sulfate with a more 34S-depleted sulfate component possibly from mineralization of RS.