Impact of different nitrogen emission sources on tree physiology as assessed by a triple stable isotope approach

The importance that nitrogen (N) deposition has in driving the carbon (C) sequestration of forests has recently been investigated using both experimental and modeling approaches. Whether increased N deposition has positive or negative effects on such ecosystems depends on the status of the N and the duration of the deposition. By combining δ¹³C, δ¹⁸O, δ¹⁵N and dendrochronological approaches, we analyzed the impact of two different sources of NO_x emissions on two tree species, namely: a broadleaved species (Quercus cerris) that was located close to an oil refinery in Southern Italy, and a coniferous species (Picea abies) located close to a freeway in Switzerland. Variations in the c_i/c_a ratio and the distinction between stomatal and photosynthetic responses to NO_x emissions in trees were assessed using a conceptual model, which combines δ¹³C and δ¹⁸O. δ¹⁵N in leaves, needles and tree rings was found to be a bioindicator of N input from anthropogenic emissions, especially at the oil refinery site. We observed that N fertilization had a stimulatory effect on tree growth near the oil refinery, while the opposite effect was found for trees at the freeway site. Changes in the c_i/c_a ratio were mostly related to variations in δ¹³C at the freeway site and, thus, were driven by photosynthesis. At the oil refinery site they were mainly related to stomatal conductance, as assessed using δ¹⁸O. This study demonstrates that a single method approach does not always provide a complete picture of which physiological traits are more affected by N emissions. The triple isotope approach combined with dendrochronological analyses proved to be a very promising tool for monitoring the ecophysiological responses of trees to long-term N deposition.     

Using atmospheric chemistry and storm track information to explain the variation of nitrate stable isotopes in precipitation at a site in central Pennsylvania,USA

Stable isotopes of NO₃^? (δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^?) were monitored in precipitation at a central Pennsylvania site during six storm events in 2005 to determine whether information on atmospheric oxidants (e.g., O₃, NO₂, and NO_x), and storm tracks (using the NOAA HYSPLIT model) were capable of explaining observed seasonal and within-storm isotopic variation. Results showed that δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^? in precipitation varied significantly during individual storm events. Seasonally, δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^? in precipitation followed a pattern of depletion during the summer months and enrichment during the winter months. NO₃^? precursor concentrations and atmospheric oxidants were useful for explaining the seasonal and within-storm variation of δ¹⁵N–NO₃^? for all six storm events as evidenced by negative relationships with NO₂:NO_x ratios and ozone (O₃). In comparison, δ¹⁸O–NO₃^? was positively related to O₃ in three dormant season storms, which suggested that the O₃ oxidation pathway was important for producing the high δ¹⁸O–NO₃^? observed in wintertime precipitation. Storm track information was especially useful for describing differences in δ¹⁵N–NO₃^?. Cool-sector storms originating from the E/NE produced slightly negative δ¹⁵N–NO₃^? values characteristic of automobile emissions, whereas warm-sector storms with tracks from the SW/S/SE produced slightly positive δ¹⁵N–NO₃^? values characteristic of coal-fired emissions. Lightning also may have been an important source of atmospheric NO₃^? during two warm-sector thunderstorms. This study showed that (1) information about oxidant levels can be useful to predict the seasonal and within-storm variation of NO₃^? stable isotopes in precipitation, and (2) knowledge of storm tracks (warm-sector versus cool-sector) may be important for determining sources of NO₃^? in wet deposition.     

Monthly variations in nitrogen isotopes of ammonium and nitrate in wet deposition at Guangzhou,south China

Monthly nitrogen isotopes of ammonium and nitrate in wet deposition in the city of Guangzhou, and the causes of their variability, are reported in this paper. Nitrate δ¹⁵N showed nearly constant values around zero in the dry season (October to April), but oscillating values from negative to positive in the rainy season (May to September). By contrast, ammonium δ¹⁵N displayed lower values during the rainy season than in the dry season. The rural area north of the city was considered as the prominent source of ammonium and nitrate in spring and early summer (May and June), as suggested by their concurrent negative isotopic trends and higher NH₄⁺/NO₃^? ratios. From July to September, different dominating sources from the city, i.e., fossil fuel combustion for nitrate, and sewage and waste emission for ammonium, caused disparate δ¹⁵N trends of the two species, showing positive nitrate δ¹⁵N, but still negative ammonium δ¹⁵N. During the cool dry season, the high values of ammonium δ¹⁵N and concurrently low NH₄⁺/NO₃^? ratios suggested the decrease in NH₃ volatilization and relatively important thermogenic origin of ammonium, but the intermediate nitrate δ¹⁵N values around zero may be a result of a balanced emission of NO_x from the city and the rural areas. The isotopic effects of chemical conversion of NO_x to nitrate and washout of nitrate were ruled out as significant causes of nitrate δ¹⁵N variability, but ammonium washout, during which ¹⁵N is assumed to be preferentially removed, may partly contribute to the ammonium δ¹⁵N variability.     

Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO_x, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O₃ and NO₂) varies with the level of NO_x, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NO_x-independent and NO_x-dependent contributions. The former is effectively a regional contribution which equates to the regional background O₃ level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO₂ emissions, (ii) the thermal reaction of NO with O₂ at high NO_x, and (iii) common-source emission of species which promote NO to NO₂ conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HO_x radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NO_x, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO₂ and O₃, are used to define expressions which describe the likely variation of annual mean NO₂ as a function of NO_x at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O₃.     

Stable isotope signatures reflect competitiveness between trees under changed CO2/O3 regimes

Here we synthesize key findings from a series of experiments to gain new insight on inter-plant competition between juvenile beech (Fagus sylvatica) and spruce (Picea abies) under the influence of increased O₃ and CO₂ concentrations. Competitiveness of plants was quantified and mechanistically interpreted as space-related resource investments and gains. Stable isotopes were addressed as temporal integrators of plant performance, such as photosynthesis and its relation to water use and nitrogen uptake. In the weaker competitor, beech, efficiency in space-related aboveground resource investment was decreased in competition with spruce and positively related to Δ¹³C, as well as stomatal conductance, but negatively related to δ¹⁸O. Likewise, our synthesis revealed that strong belowground competition for water in spruce was paralleled in this species by high N assimilation capacity. We suggest combining the time-integrative potential of stable isotopes with space-related investigations of competitiveness to accomplish mechanistic understanding of plant competition for resources.     

Analysis of a Farquhar-von Caemmerer-Berry leaf-level photosynthetic rate model for Populus tremuloides in the context of modeling and measurement limitations

The balance of mechanistic detail with mathematical simplicity contributes to the broad use of the Farquhar, von Caemmerer and Berry (FvCB) photosynthetic rate model. Here the FvCB model was coupled with a stomatal conductance model to form an [A,g_s] model, and parameterized for mature Populus tremuloides leaves under varying CO₂ and temperature levels. Data were selected to be within typical forest light, CO₂ and temperature ranges, reducing artifacts associated with data collected at extreme values. The error between model-predicted photosynthetic rate (A) and A data was measured in three ways and found to be up to three times greater for each of two independent data sets than for a base-line evaluation using parameterization data. The evaluation methods used here apply to comparisons of model validation results among data sets varying in number and distribution of data, as well as to performance comparisons of [A,g_s] models differing in internal-process components.     

Nitrogen Dioxide and Nitric Oxide in Non-Urban Air

Measurement of NO₂ and NO has been carried out in Piedmont, N. C. and in the southern Appalachian Mountains. Average values for the Piedmont were: continuous NO₂ measured 30 ft above surface, 0.76 pphm (14.3 μg/m³), 1 20 ft, 0.61 pphm (11.5 μg/m³); simultaneous values (also Piedmont) (2-hr discrete samples) taken at an earlier time at 4 ft, NO₂, 0.56 pphm (10.6 μg/m³), NO, 0.19 pphm (2.34 μg/m³). The mountain top values (5120 ft, 1573 m) were: NO₂, 0.46 pphm (6.4 μg/m³), NO, 0.26 pphm (2.72 μg/m³). The results of this study furnish further proof that tropospheric NO and NO₂ are produced at the surface of the earth. Data obtained are consistent with the belief that a major sink for NO_x is reaction with O3 and ultimate conversion to nitrate.

Ozone values frequently increased and NO_x values decreased ahead of cold fronts, probably as a result of deep vertical mixing. Also, in small scale turbulence the changes in NO_x values and in the O₃ values tended to be “out of phase,” i.e., as O₃ concentration increased, NO_x concentration decreased and vice versa. Values of NO_x from Green Knob, N. C. (mountain top) also tended to be higher at times when O₃ values were lowest.

The NO₂ hourly average values in Piedmont, N. C, demonstrated a diurnal cycle reminiscent of diurnal urban changes. An early morning peak was followed by a minimum in mid-afternoon. Next, the values rose to a broad evening peak and then decreased slowly during the night. Reported urban concentrations are usually about ten times those found in Piedmont, N. C.     

Atmospheric transport of urban-derived NH(x): Evidence from nitrogen concentration and delta(15)N in epilithic mosses at Guiyang, SW China

Nitrogen concentration and δ¹⁵N 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 δ¹⁵N revealed that atmospheric N deposition is dominated by NH_x-N from two major sources (urban sewage NH₃ and agricultural NH₃), the deposition of urban-derived NH_x followed a point source pattern characterized by an exponential decline with distance from the urban center, while the agricultural-derived NH_x 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 NH_x averaged 41 km from the urban center, and it could be determined from the relationship between moss δ¹⁵N and distance [y = 2.54 ln(x) − 12.227] that urban-derived NH_x was proportionally lower than agricultural-derived NH_x in N deposition at sites beyond 17.2 km from the urban center. Consequently, the variation of urban-derived NH_x with distance from the urban center could be modeled as y = 56.272e^−0.116x − 0.481 in the Guiyang area.     

Regenerative Thermal Oxidation of Airborne N,N-Dimethylformamide and Its Associated Nitrogen Oxides Formation Characteristics

Abstract

In this study, a two-bed electrically heated regenerative thermal oxidizer (RTO) was used to test the thermal destruction and oxides of nitrogen (NO_x) formation characteristics in burning airstreams that contain either N, N-dimethylformamide or dimethylformamide (DMF) mixed with methyl ethyl ketone (MEK). The RTO contained two 0.152 m × 0.14 m × 1 m (L × W times] H) beds, both packed with gravel particles with an average diameter of approximately 0.0111 m and a height of up to 1 m with a void fraction of 0.42 in the packed section. The thermal recovery efficiency (TRE) and the gas pressure drop over the beds were also studied. Experimental results reveal that, with a valve shifting time (t _s) of 1.5 min, a superficial gas velocity (U _g) of 0.39 m/sec (evaluated at an influent air temperature of around 30 °C) and preset maximum destruction temperatures (T _S) of 750–950 °C, no NO_x was present in the effluent gas from the RTO when it was loaded with DMF-free air. When only DMF was present in the influent air, the average destruction efficiencies exceeded 96%, and increased with the influent DMF concentration from 300 to 750 mg/N?m³. The “NO_x-N formation/DMF-N destruction” mass ratios were in the range 0.76–1.05, and decreased as the influent DMF concentration increased within the experimental range. When both DMF and MEK were present in the influent gas, the NO_x formation ratio was almost the same and the DMF destruction efficiency increased with the influent MEK/DMF ratio from 150/300 to 4500/300 (mg/mg) and in the preset temperature range. The NO_x formation ratios were in the range 0.75–0.96. The TRE decreased as U _g increased but was invariant with T _s. The Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.     

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 δ¹⁵N values were observed in the camphor leaves, especially in old leaves of upper canopies, and ?δ¹⁵N = δ¹⁵N_upper − δ¹⁵N_lower > 0, while those near the industrial area had more negative δ¹⁵N values and ?δ¹⁵N < 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 ¹⁵N-depleted NH_y in atmospheric deposition by leaves at sites near the industrial area. This study presents novel evidence that ¹⁵N natural abundance of camphor leaves can be used as a robust indicator of atmospheric N sources.     

A new measurement method for nitrogen oxides in the air using an annular diffusion scrubber coated with titanium dioxide

A new convenient measurement method of nitrogen oxides (NO_x) in the ambient air was developed. The collection of NO_x is performed by an annular diffusion scrubber coated with a mixture of titanium dioxide (TiO₂) and hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) and the analysis is carried out by ion chromatography with conductivity detection. Under ultraviolet light (UV) illumination, TiO₂ produces reactive oxygen species such as super oxide (O₂⁻), hydroxyl radical (OH·) and peroxyhydroxyl radical (HO₂·), by which nitric oxide (NO) is oxidized to nitrogen dioxide (NO₂), and is further oxidized to nitric acid (HNO₃). The yielded HNO₃ and NO₂ are effectively adsorbed on the surface of TiO₂ and hydroxyapatite. The collection efficiencies of NO and NO₂ by the annular diffusion scrubber coated with the catalysts under UV illumination are higher than 98%, respectively, at the air flow rate of 0.2–1.0 l min⁻¹. After the collection of NO_x, by feeding deionized water into the annular diffusion scrubber, HNO₃ and NO₂ which adsorbed on the catalysts are extracted as forms of nitrite ion (NO₂⁻) and nitrate ion (NO₃⁻). The extraction efficiencies of NO and NO₂ are almost 100%. The activity of the washed catalysts can be completely recovered by drying with the purified air. Further, a simultaneous separated measurement of NO and NO₂ can be performed by utilizing the UV illumination dependence. This method was applied to the measurement of NO_x in the ambient air. The NO_x concentration measured by this method was in good agreement with that obtained using the chemiluminescence NO_x analyzer.     

Diurnal changes in photosynthetic parameters of Populus tremuloides, modulated by elevated concentrations of CO2 and/or O3 and daily climatic variation

The diurnal changes in light-saturated photosynthesis (Pn) under elevated CO₂ and/or O₃ in relation to stomatal conductance (g_s), water potential, intercellular [CO₂], leaf temperature and vapour-pressure difference between leaf and air (VPD_L) were studied at the Aspen FACE site. Two aspen (Populus tremuloides Michx.) clones differing in their sensitivity to ozone were measured. The depression in Pn was found after 10:00 h. The midday decline in Pn corresponded with both decreased g_s and decreased Rubisco carboxylation efficiency, Vc_max. As a result of increasing VPD_L, g_s decreased. Elevated [CO₂] resulted in more pronounced midday decline in Pn compared to ambient concentrations. Moreover, this decline was more pronounced under combined treatment compared to elevated CO₂ treatment.The positive impact of CO₂ on Pn was relatively more pronounced in days with environmental stress but relatively less pronounced during midday depression. The negative impact of ozone tended to decrease in both cases.     

Stomatal uptake of O3 in aspen and aspen-birch forests under free-air CO2 and O3 enrichment

Rising atmospheric carbon dioxide (CO₂) may alleviate the toxicological impacts of concurrently rising tropospheric ozone (O₃) during the present century if higher CO₂ is accompanied by lower stomatal conductance (g_s), as assumed by many models. We investigated how elevated concentrations of CO₂ and O₃, alone and in combination, affected the accumulated stomatal flux of O₃ (AFst) by canopies and sun leaves in closed aspen and aspen-birch forests in the free-air CO₂-O₃ enrichment experiment near Rhinelander, Wisconsin. Stomatal conductance for O₃ was derived from sap flux data and AFst was estimated either neglecting or accounting for the potential influence of non-stomatal leaf surface O₃ deposition. Leaf-level AFst (AFst_l) was not reduced by elevated CO₂. Instead, there was a significant CO₂ × O₃ interaction on AFst_l, as a consequence of lower values of g_s in control plots and the combination treatment than in the two single-gas treatments. In addition, aspen leaves had higher AFst_l than birch leaves, and estimates of AFst_l were not very sensitive to non-stomatal leaf surface O₃ deposition. Our results suggest that model projections of large CO₂-induced reductions in g_s alleviating the adverse effect of rising tropospheric O₃ may not be reasonable for northern hardwood forests.     

Application of 15N–18O double stable isotope tracer technique in an agricultural nonpoint polluted river of the Yangtze Delta Region

One strategy to combat nitrate (NO₃-N) contamination in rivers is to understand its sources. NO₃-N sources in the East Tiaoxi River of the Yangtze Delta Region were investigated by applying a ¹⁵N–¹⁸O dual isotope approach. Water samples were collected from the main channel and from the tributaries. Results show that high total N and NO₃-N are present in both the main channel and the major tributaries, and NO₃-N was one of the most important N forms in water. Analysis of isotopic compositions (δ ¹⁸O, δD) of water suggests that the river water mainly originated from three tributaries during the sampling period. There was a wide range of δ ¹⁵N-NO₃ (?1.4 to 12.4 ‰) and a narrow range of δ ¹⁸O-NO₃ (3.7 to 9.0 ‰) in the main channel waters. The δ ¹⁵N and δ ¹⁸O-NO₃ values in the upper, middle, and lower channels along the river were shifted as 8.2, 3.5, and 9.5 ‰, and 9.0, 4.2, and 6.0 ‰, respectively. In the tributary South Tiao, the δ ¹⁵N and δ ¹⁸O-NO₃ values were as high as 9.5 and 7.0 ‰, while in the tributaries Mid Tiao and North Tiao, NO₃-N in most of the samples had relatively low δ ¹⁵N and δ ¹⁸O-NO₃ values from 2.3 to 7.5 ‰ and 4.7 to 7.0 ‰, separately. Our results also suggest that the dual isotope approach can help us develop the best management practice for relieving NO₃-N pollution in the rivers at the tributary scale.     

Nitrogen oxide fluxes between corn (Zea mays L.) leaves and the atmosphere

In the United States, fertilized corn fields, which make up approximately 5% of the total land area, account for approximately 45% of total soil NO_x emissions. Leaf chamber measurements were conducted of NO and NO₂ fluxes between individual corn leaves and the atmosphere in (1) field-grown plants near Champaign, IL (USA) in order to assess the potential role of corn canopies in mitigating soil–NO_x emissions to the atmosphere, and (2) greenhouse-grown plants in order to study the influence of various environmental variables and physiological factors on the dynamics of NO₂ flux. In field-grown plants, fluxes of NO were small and inconsistent from plant to plant. At ambient NO concentrations between 0.1 and 0.3 ppbv, average fluxes were zero. At ambient NO concentrations above 1 ppbv, NO uptake occurred, but fluxes were so small (14.3±0.0 pmol m⁻² s⁻¹) as to be insignificant in the NO_x inventory for this site. In field-grown plants, NO₂ was emitted to the atmosphere at ambient NO₂ concentrations below 0.9 ppbv (the NO₂ compensation point), with the highest rate of emission being 50 pmol m⁻² s⁻¹ at 0.2 ppbv. NO₂ was assimilated by corn leaves at ambient NO₂ concentrations above 0.9 ppbv, with the maximum observed uptake rate being 643 pmol m⁻² s⁻¹ at 6 ppbv. When fluxes above 0.9 ppbv are standardized for ambient NO₂ concentration, the resultant deposition velocity was 1.2±0.1 mm s⁻¹. When scaled to the entire corn canopy, NO₂ uptake rates can be estimated to be as much as 27% of the soil-emitted NO_x. In greenhouse-grown and field-grown leaves, NO₂ deposition velocity was dependent on incident photosynthetic photon flux density (PPFD; 400–700 nm), whether measured above or below the NO₂ compensation point. The shape of the PPFD dependence, and its response to ambient humidity in an experiment with greenhouse-grown plants, led to the conclusion that stomatal conductance is a primary determinant of the PPFD response. However, in field-grown leaves, measured NO₂ deposition velocities were always lower than those predicted by a model solely dependent on stomatal conductance. It is concluded that NO₂ uptake rate is highest when N availability is highest, not when the leaf deficit for N is highest. It is also concluded that the primary limitations to leaf-level NO₂ uptake concern both stomatal and mesophyll components.     

Tissue S/N ratios and stable isotopes (δS and δN) 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 SO₄²⁻/NH₄⁺ ratios, each people SO₂ 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 δ³⁴S and NH₄⁺-N wet deposition, respectively, indicating that local coal and animal NH₃ are the major atmospheric S and N sources.     

Chemistry of HOx radicals in the upper troposphere

Aircraft observations from three recent missions (STRAT, SUCCESS, SONEX) are synthesized into a theoretical analysis of the factors controlling the concentrations of HO_x radicals (HO_x=OH+peroxy) and the larger reservoir family HO_y (HO_y=HO_x+2H₂O₂+2CH₃OOH+HNO₂+HNO₄) in the upper troposphere. Photochemical model calculations capture 66% of the variance of observed HO_x concentrations. Two master variables are found to determine the variance of the 24 h average HO_x concentrations: the primary HO_x production rate, P(HO_x), and the concentration of nitrogen oxide radicals (NO_x=NO+NO₂). We use these two variables as a coordinate system to diagnose the photochemistry of the upper troposphere and map the different chemical regimes. Primary HO_x production is dominated by the O(¹D)+H₂O reaction when [H₂O]>100 ppmv, and by photolysis of acetone (and possibly other convected HO_x precursors) under drier conditions. For the principally northern midlatitude conditions sampled by the aircraft missions, the HO_x yield from acetone photolysis ranges from 2 to 3. Methane oxidation amplifies the primary HO_x source by a factor of 1.1–1.9. Chemical cycling within the HO_x family has a chain length of 2.5–7, while cycling between the HO_x family and its HO_y reservoirs has a chain length of 1.6–2.2. The number of ozone molecules produced per HO_y molecule consumed ranges from 4 to 12, such that ozone production rates vary between 0.3 and 5 ppbv d⁻¹ in the upper troposphere. Three chemical regimes (NO_x-limited, transition, NO_x-saturated) are identified to describe the dependence of HO_x concentrations and ozone production rates on the two master variables P(HO_x) and [NO_x]. Simplified analytical expressions are derived to express these dependences as power laws for each regime. By applying an eigenlifetime analysis to the HO_x–NO_x–O₃ chemical system, we find that the decay of a perturbation to HO_y in the upper troposphere (as from deep convection) is represented by four dominant modes with the longest time scale being factors of 2–3 times longer than the steady-state lifetime of HO_y.     

In situ measurements of HNO3, NOy,NO, and O3 in the lower stratosphere and upper troposphere

In situ measurements of nitric acid (HNO₃), reactive nitrogen (NO_y), nitric oxide (NO), and ozone (O₃) made in the upper troposphere (UT) and lower stratosphere (LS) between 29° and 33°N latitudes during September 1999 are used to examine NO_y partitioning and correlations between the measured species in these regions. The fast-response (1 s) HNO₃ measurements are acquired with a new autonomous CIMS instrument. In the LS, HNO₃ accounts for the majority of NO_y, and the sum of HNO₃ and NO_x accounts for approximately 90% of NO_y. In the UT, the sum of HNO₃ and NO_x varies between 40% and 100% of NO_y. Both HNO₃ and NO_y are strongly positively correlated with O₃, with larger correlation slopes in the UT than in the LS. In the UT at low values of the quantity (NO_y–NO_x–HNO₃), it is uncorrelated with O₃, while at higher values, a positive correlation with O₃ is found. Of these two air mass types, those with higher (NO_y–NO_x–HNO₃) mixing ratios are likely associated with the presence of peroxyacetyl nitrate (PAN) that is produced by NO_x-hydrocarbon chemistry.     

石家庄市道路交通环境NO_x污染水平及ARMA模型预测

选择石家庄市区代表性路段作为研究对象,对其交通环境空气中NOx的污染水平进行现状监测。基于Matlab软件建立拟合模型,对下一时期的NOx污染趋势进行预测。结果表明,石家庄市交通环境中NOx小时浓度介于0.047~0.237 mg/m3之间,呈早晚高,且下午明显低于上午的日变化规律;NOx日均浓度介于0.076~0.211 mg/m3之间,其浓度与车流量呈明显的正相关性。利用matlab软件建立的ARMA模型能够较好地预测道路交通环境空气中NOx的浓度变化趋势。     

The use of experimental data and their uncertainty for assessing ozone photochemistry in the Eastern Iberian Peninsula

Observation-based methods are useful tools to explore the sensitivity of ozone concentrations to precursor controls. With the aim of assessing the ozone precursor sensitivity in two locations: Paterna (suburban) and Villar del Arzobispo (rural) of the Turia river basin in the east of Spain, the photochemical indicator O₃/NO_y and the Extent-of-Reaction (EOR) parameter have been calculated from field measurements. In Paterna, the O₃/NO_y ratio varied from 0 to 13 with an average value of 5.1 (SD 3.2), whereas the averaged value for the EOR was 0.43 (SD 0.14). In Villar del Arzobispo, the O₃/NO_y ratio changed from 5 to 30 with a mean value of 13.6 (SD 4.7) and the EOR gave an averaged value of 0.72 (SD 0.11). The results show two different patterns of ozone production as a function of the location. The suburban area shows a VOC-sensitive regime whereas the rural one shows a transition regime close to NO_x-sensitive conditions. No seasonal differences in these regimes are observed along the monitoring campaigns. Finally, an analysis of the influence of the measurement quality of NO_y, NO_x and O₃ on the uncertainty of the O₃/NO_y ratio and the EOR was performed showing that the uncertainty of O₃/NO_y is not dependent on either its value or the individual values of O₃ and NO_y but just on the quality of O₃ and NO_y measurements. The maximum uncertainty is 26% as long as the combined uncertainties of O₃ and NO_y remain below the 7.5%. The case of the EOR is different and its uncertainty depends on both the value of the EOR parameter and the individual concentration values of NO_y and NO_x. The uncertainty of the EOR estimation can be very high (>200%) if the combined uncertainties of both NO_y and NO_x are high (>7.5%), or especially, if u(NO_y) and u(NO_x) differ considerably from each other (>3.5%).