An instrument for semi-continuous monitoring of the size-distribution of nitrate,ammonium, sulphate and chloride in aerosol

An instrument was developed for semi-continuous measurement of the size-distribution of submicron nitrate, ammonium, sulphate and chloride. Novel in the instrumentation is the size-classification, which is realised with a pre-separator that consists of a set of four parallel impactors. The cut-off diameters of the impactors are at 0.18, 0.32, 0.56 and 1.0 μm. Aerosols smaller than the associated cut-off size pass the respective impactor and arrive in the detector. The manifold with impactors contains two additional lines, one open line and one containing a filter that removes all aerosols. This latter line provides an on-line field-blank. The sample air-flow is automatically switched by wide-bore ball valves to one of the six sampling lines for a period of 20 min; a measuring cycle thus takes 2 h.Down-stream of the pre-separator the sampling and automated on-line analysis of the transmitted aerosol is accomplished with a “MARGA”. In this instrument steam condensation is used to grow the aerosol. The droplets formed are collected in a cyclone that drains to wet-chemical analysis systems. A wet-denuder between pre-separator and collector removes interfering gases, like nitric acid and ammonia. This enables artefact-free and thus representative semi-continuous measurement of the size-distribution of the semi-volatile (ammonium) nitrate.The novel MARGA-sizer was first used in a 1 week field-test. After modifications it was then deployed in a monitoring campaign of 2 months in the summer of 2002, at the top level of the meteo-tower of Cabauw in the centre of the Netherlands. The high location, 200 m, was chosen to obtain data on ammonium nitrate that are minimally affected by surface emissions of ammonia. The data coverage over the period was over 60%; failure of the instrumentation was mainly associated with spells of extreme solar heating of the tower and associated high temperatures inside.The average concentration of nitrate was 2.6 μg m⁻³, which was very similar to the value interpolated from data in the national network. The mass concentration of submicron nitrate was 2.0 μg m⁻³, of which 46% was in particles smaller than 0.32 μm. To put this in perspective: the concentration of submicron sulphate was similar to that of nitrate, while 53% was in particles smaller than 0.32 μm. The ion balance showed that the compounds were present as the fully neutralised salts. Quite large diurnal variations were observed for nitrate, with a surprising maximum in the afternoon. The size-distribution of the semi-volatile nitrate was rather constant over a daily cycle.     

Control of ammonia toxicity to Hyalella azteca by sodium, potassium and pH

The toxicity of ammonia to Hyalella azteca at constant pH in artificial media was controlled by sodium and potassium, and not by calcium, magnesium, or anions. Small increases in the LC50 for total ammonia (from 0.15 to 0.5 mM) occurred as sodium was increased from 0.1 to 1 mM and above, but major increases in the LC50 (to over 10 mM total ammonia) required the addition of potassium. Potassium was, however, more effective at reducing ammonia toxicity at high (1 mM) sodium than at low (0.1 mM) sodium. Ammonia toxicity was independent of pH at low sodium and potassium concentrations, when ammonia toxicity appeared to be associated primarily with aqueous ammonium ion concentrations. At high sodium and potassium concentrations, the toxicity of ammonia was reduced to the point where un-ionized ammonia concentrations also affected toxicity, and the LC50 became pH dependent. A mathematical model was produced for predicting ammonia toxicity from sodium and potassium concentrations and pH.     

The wet deposition of sulphate and its relationship to sulphur dioxide emissions

The factors that need to be considered when comparing rainfall data with emission data are summarized, and it is indicated that trend analysis cannot be done properly without the use of a transport model. An optimization procedure is then used to fit the Fisher statistical model to European sulphate in rain data. This indicates moderately efficient to efficient wet removal of sulphate on average across Europe which is consistent with limited aqueous oxidation close to major source areas and a more linear behaviour at greater distances. At such distances, particularly in remote high rainfall areas, the results demonstrate the importance of ‘background’ sulphate. The results are all consistent with the latest U.K. rainfall data.     

Quantitative determination of sulphate in individual aerosol particles

The vapour-deposited thin-film method of analysing individual aerosol particles is shown to provide a method for quantitative determination of sulphate. The method utilizes a calibration curve which relates the mass of sulphate in a particle to the diameter of the reaction ring it produces with a thin layer of barium chloride. A single calibration curve was shown to apply to ammonium sulphate, sulphuric acid and mixed ammonium sulphate/sodium chloride particles. Masses of as little as 10⁻¹⁷ g sulphate, corresponding to particle diameters of ~0.03 μm, were determined to +41%, −29% accuracy with this technique.     

Dry deposition of ammonia,nitric acid,ammonium, and nitrate to alpine tundra at Niwot Ridge,Colorado

Micrometeorological measurements and ambient air samples, analyzed for concentrations of NH₃, HNO₃, NH₄⁺, and NO₃⁻, were collected at an alpine tundra site on Niwot Ridge, Colorado. The measured concentrations were extremely low and ranged between 5 and 70 ng N m⁻³. Dry deposition fluxes of these atmospheric species were calculated using the micrometeorological gradient method. The calculated mean flux for NH₃ indicates a net deposition to the surface and indicates that NH₃ contributed significantly to the total N deposition to the tundra during the August–September measurement period. Our pre-measurement estimate of the compensation point for NH₃ in air above the tundra was 100–200 ng N m⁻³; thus, a net emission of NH₃ was expected given the low ambient concentrations of NH₃ observed. Based on our results, however, the NH₃ compensation point at this alpine tundra site appears to have been at or below about 20 ng N m⁻³. Large deposition velocities (>2 cm s⁻¹) were determined for nitrate and ammonium and may result from reactions with surface-derived aerosols.     

Trends in on-road vehicle emissions of ammonia

Motor vehicle emissions of ammonia have been measured at a California highway tunnel in the San Francisco Bay area. Between 1999 and 2006, light-duty vehicle ammonia emissions decreased by 38 ± 6%, from 640 ± 40 to 400 ± 20 mg kg^?1. High time resolution measurements of ammonia made in summer 2001 at the same location indicate a minimum in ammonia emissions correlated with slower-speed driving conditions. Variations in ammonia emission rates track changes in carbon monoxide more closely than changes in nitrogen oxides, especially during later evening hours when traffic speeds are highest. Analysis of remote sensing data of Burgard et al. (Environmental Science Technology 2006, 40, 7018–22) indicates relationships between ammonia and vehicle model year, nitrogen oxides, and carbon monoxide. Ammonia emission rates from diesel trucks were difficult to measure in the tunnel setting due to the large contribution to ammonia concentrations in a mixed-traffic bore that were assigned to light-duty vehicle emissions. Nevertheless, it is clear that heavy-duty diesel trucks are a minor source of ammonia emissions compared to light-duty gasoline vehicles.     

The mass accommodation coefficient of ammonium nitrate aerosol

The mass transfer rate of pure ammonium nitrate between the aerosol and gas phases was quantified experimentally by the use of the tandem differential mobility analyzer/scanning mobility particle sizer (TDMA/SMPS) technique. Ammonium nitrate particles 80–220 nm in diameter evaporated in purified air in a laminar flow reactor under temperatures of 20–27°C and relative humidities in the vicinity of 10%. The evaporation rates were calculated by comparing the initial and final size distributions. A theoretical expression of the evaporation rate incorporating the Kelvin effect and the effect of relative humidity on the equilibrium constant is developed. The measurements were consistent with the theoretical predictions but there was evidence of a small kinetic resistance to the mass transfer rate. The discrepancy can be explained by a mass accommodation coefficient ranging from 0.8 to 0.5 as temperature increases from 20–27°C. The corresponding timescale of evaporation for submicron NH₄NO₃ particles in the atmosphere is of the order of a few seconds to 20 min.     

Coral reef aerosol emissions in response to irradiance stress in the Great Barrier Reef,Australia

We investigate the correlation between stress-related compounds produced by corals of the Great Barrier Reef (GBR) and local atmospheric properties—an issue that goes to the core of the coral ecosystem’s ability to survive climate change. We relate the variability in a satellite decadal time series of fine-mode aerosol optical depth (AOD) to a coral stress metric, formulated as a function of irradiance, water clarity, and tide, at Heron Island in the southern GBR. We found that AOD was correlated with the coral stress metric, and the correlation increased at low wind speeds, when horizontal advection of air masses was low and the production of non-biogenic aerosols was minimal. We posit that coral reefs may be able to protect themselves from irradiance stress during calm weather by affecting the optical properties of the atmosphere and local incident solar radiation.     

Direct wet and dry deposition of ammonia,nitric acid,ammonium and nitrate to the Tampa Bay Estuary,FL, USA

The average total (wet plus dry) nitrogen deposition to the Tampa Bay Estuary was 7.3 (±1.3) kg-N ha⁻¹ yr⁻¹ or 760 (±140) metric tons-N yr⁻¹ for August 1996–July 1999, estimated as a direct deposition rate to the 104,000-ha water surface. This nitrogen flux estimate accounted for ammonia exchange at the air–sea interface. The uncertainty estimate was based on measurement error. Wet deposition was 56% of the total nitrogen deposition over this period, with an average 0.78 ratio of dry-to-wet deposition. Wet nitrogen deposition rates varied considerably, from near zero to 1.3 kg-N ha⁻¹ month⁻¹. About 40% of the total nitrogen flux occurred during the summer months of June, July and August when rainfall was the highest, except for 1997–1998 when the El Niño phenomenon brought unseasonal rainfall. Ammonia/ammonium contributed to 58%, and nitric acid/nitrate 42%, of the total nitrogen deposition over the 3-yr period. In one summer as waters of Tampa Bay warmed above 28°C and ammonium concentrations reached 0.03 mg l⁻¹, the estimated net flux of ammonia was from the Bay waters to the atmosphere.     

Measurement and analysis of atmospheric ammonia emissions from anaerobic lagoons

Ammonia-nitrogen flux (NH₃-N=(14/17)NH₃) was determined from six anaerobic swine waste storage and treatment lagoons (primary, secondary, and tertiary) using the dynamic chamber system. Measurements occurred during the fall of 1998 through the early spring of 1999, and each lagoon was examined for approximately one week. Analysis of flux variation was made with respect to lagoon surface water temperature (∼15 cm below the surface), lagoon water pH, total aqueous phase NH_x(=NH₃+NH₄⁺) concentration, and total Kjeldahl nitrogen (TKN). Average lagoon temperatures (across all six lagoons) ranged from approximately 10.3 to 23.3^°C. The pH ranged in value from 6.8 to 8.1. Aqueous NH_x concentration ranged from 37 to 909 mg N l⁻¹, and TKN varied from 87 to 950 mg N l⁻¹. Fluxes were the largest at the primary lagoon in Kenansville, NC (March 1999) with an average value of 120.3 μg N m⁻² min⁻¹, and smallest at the tertiary lagoon in Rocky Mount, NC (November 1998) at 40.7 μg N m⁻² min⁻¹. Emission rates were found to be correlated with both surface lagoon water temperature and aqueous NH_x concentration. The NH₃-N flux may be modeled as ln(NH₃-N flux)=1.0788+0.0406T_L+0.0015([NH_x]) (R²=0.74), where NH₃-N flux is the ammonia flux from the lagoon surface in μg N m⁻² min⁻¹, T_L is the lagoon surface water temperature in ^°C, and [NH_x] is the total ammonia-nitrogen concentration in mg N l⁻¹.     

氨法脱硫洗涤液pH的计算模型

应用酸碱质子理论,根据质子平衡方程建立了氨法脱硫洗涤液相关离子浓度与pH的相关性模型,并对其影响因素进行了讨论。研究表明:脱硫洗涤液理论计算pH与实测的pH基本吻合。结合实验验证了影响洗涤液pH的硫元素存在形态与脱硫洗涤液pH之间的相图关系,并提出模型修正方法。模型可作为氨法脱硫洗涤液pH的合理计算方法。     

Measurement of aerosol size distributions for nitrate and major ionic species

Nitrate particle size distributions were determined at the Nitrogen Species Methods Comparison Study at Claremont, CA during September 1985 with the Berner nine stage cascade impactor. Particle bounce was minimized by an inert fluorocarbon grease substrate. Interference from nitric acid was eliminated with a vertical acid gas denuder designed to prevent large particle loss. Samples were taken with and without the grease or denuder to test the techniques. Volatile nitrate loss was less than 10%, based on comparisons with fine nitrate from parallel filter samplers.Aerosol size distributions for the major ionic species were determined under varying atmospheric conditions and good ion balances achieved. Nitrate was bimodal during both day and night-time periods. Fine mode nitrate was associated with ammonium while coarse mode nitrate was associated with both ammonium and sodium. Extensive evidence including size distributions, temporal associations and species balances is given for the reaction of nitric acid and sea salt to produce hydrochloric acid and coarse mode nitrate. Sulfate was primarily in two submicrometer modes. Strong acid was associated with the smaller sulfate mode.     

双系统离子色谱同时测定河流中氨氮、亚硝酸盐和硝酸盐的含量

水样经o.22μm微孔滤膜过滤后,通过双系统离子色谱,分别以氢氧化钾和甲烷磺酸作为流动相,抑制电导检测,成功建立了同时、准确、快速测定河流中氨氮、亚硝酸盐和硝酸盐的方法.结果表明,该方法检出限o.001～0.002 mg/L,相对标准偏差1.2％～1.9％,加标回收率89.6％～101.5％.该方法操作简便、快速、选择性好,检出限可满足环境水质分析的要求.     

The use of ambient measurements to identify which precursor species limit aerosol nitrate formation

A thermodynamic equilibrium model was used to investigate the response of aerosol NO3 to changes in concentrations of HNO3, NH3, and H2SO4. Over a range of temperatures and relative humidities (RHs), two parameters provided sufficient information for indicating the qualitative response of aerosol NO3. The first was the excess of aerosol NH4+ plus gas-phase NH3 over the sum of HNO3, particulate NO3, and particulate SO4(2-) concentrations. The second was the ratio of particulate to total NO3 concentrations. Computation of these quantities from ambient measurements provides a means to rapidly analyze large numbers of samples and identify cases in which inorganic aerosol NO3 formation is limited by the availability of NH3. Example calculations are presented using data from three field studies. The predictions of the indicator variables and the equilibrium model are compared.     

Anthropogenic sulphate aerosol from India: estimates of burden and direct radiative forcing

A one-box chemical-meteorological model had been formulated to make preliminary estimates of sulphate aerosol formation and direct radiative forcing over India. Anthropogenic SO₂ emissions from India, from industrial fuel use and biomass burning, were estimated at 2.0 Tg S yr^-1 for 1990 in the range of previous estimates of 1.54 and 2.55 Tg S yr ^-1 for 1987. Meteorological parameters for 1990 from 18 Indian Meteorological Department stations were used to estimate spatial average sulphate burdens through formation from SO₂ reactions in gas and aqueous phase and removal by dry and wet deposition. The hydrogen peroxide reaction was found dominating for undepleted oxidant-rich conditions. Monthly mean sulphate burdens ranged from 2–10 mg m^-2 with a seasonal variation of winter–spring highs and summer lows in agreement with previous GCM studies. The sulphate burdens are dominated by sulphate removal rates by wet deposition, which are high in the monsoon period from June–November. Monthly mean direct radiative forcing from sulphate aerosols is high (−3.5 and −2.3 W m^-2) in December and January, is moderate (−1.3 to −1.5 W m^-2) during February to April and November and low (−0.4 to −0.6 W m^-2) during May to October also in general agreement with previous GCM estimates. This model, in reasonable agreement with detailed GCM results, gives us a simple tool to make preliminary estimates of sulphate burdens and direct radiative forcing.     

Quantifying emissions of primary biological aerosol particle mass in Europe

Atmospheric concentration measurements of tracers for primary biological aerosol particles (PBAPs) have been used to obtain estimates of their release into the atmosphere. Emission flux data of surrogate compounds, for which concurrent concentration measurements were available, were used to quantify the release of PBAPs as PM₁₀ mass. Results indicate fungal spores to be the most important contributors. One other main source is plant debris. Area-based emission rates of 24 kg km^?2 and year (range 6–90) have been assessed. Results scaled for Europe indicate a contribution of PBAPs to PM₁₀ concentrations in the low percentage range, with a maximum in summer when concentration levels are small. This is consistent with the range of measurements. Despite of the large uncertainties, results contribute to clarify the potential contribution of biological particles to global load of particle mass.     

Comparisons of coarse-mode aerosol nitrate and ammonium at two polluted coastal sites

Direct atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters and can be enhanced by heterogeneous reactions between gaseous atmospheric nitrogen species and aerosol sea salt, which increase deposition rates. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland. Major-ion aerosol concentrations were determined and temporal patterns were interpreted with the use of air-mass back trajectories. Low levels of terrestrially derived material were seen during periods of clean, onshore flow, with respective concentration ranges for nitrate and ammonium of 0.47–220 and below detection limit to 340 nmol m⁻³. Corresponding levels of marine derived material during these periods were high, with sodium concentrations ranging from 39 to 1400 nmol m⁻³. Highest levels of terrestrially derived material were seen during polluted, offshore flow, where the air had passed recently over strong source regions of the UK and northern Europe, with concentration ranges of nitrate and ammonium of 5.6–790 and 9.7–1000 nmol m⁻³, respectively. During polluted flow ∼40–60% of the nitrate was found in the coarse mode (>1 μm diameter) and under clean marine conditions almost 100% conversion was seen. In addition, our data suggests strong evidence for dissolution/coagulation processes that also shift nitrate to the coarse mode. Furthermore, such processes are thought also to give rise to the size-shifting of aerosol ammonium, since significant coarse-mode fractions of this species (∼19–45%) were seen at both sites. A comparison of the relative importance of nitrate and ammonium in the overall dry deposition of inorganic fixed-nitrogen at each site indicates that at Weybourne the mass-weighted dry deposition velocity of the latter is around double that seen at Mace Head with its resultant contribution to the overall inorganic nitrogen dry flux exceeding that of nitrate.     

Modelling the spatial distribution of ammonia emissions in the UK

Ammonia emissions (NH3) are characterised by a high spatial variability at a local scale. When modelling the spatial distribution of NH3 emissions, it is important to provide robust emission estimates, since the model output is used to assess potential environmental impacts, e.g. exceedance of critical loads. The aim of this study was to provide a new, updated spatial NH3 emission inventory for the UK for the year 2000, based on an improved modelling approach and the use of updated input datasets. The AENEID model distributes NH3 emissions from a range of agricultural activities, such as grazing and housing of livestock, storage and spreading of manures, and fertilizer application, at a 1-km grid resolution over the most suitable landcover types. The results of the emission calculation for the year 2000 are analysed and the methodology is compared with a previous spatial emission inventory for 1996.     

Estimating the potential for ammonia emissions from livestock excreta and manures

This paper reports a desk study to quantify the total-nitrogen (N) and ammoniacal-N contents of livestock excreta, and to compare them with estimates of N losses to the environment from that excreta. Inventories of ammonia (NH3), nitrous oxide (N2O), dinitrogen (N2), and nitric oxide emissions (NO), together with estimates of nitrate (NO3-) leaching and crop N uptake were collated. A balance sheet was constructed to determine whether our estimates of N in livestock excreta were consistent with current estimates of N losses and crop N uptake from that N, or whether emissions of N compounds from livestock excreta may have been underestimated. Total N excretion by livestock in England and Wales (E&W) was estimated as 767-816 x 10(3) t of which 487-518 x 10(3) t was estimated to be total ammoniacal-N (TAN). Estimates of NH3 and N2O losses during housing and storage were derived from the difference between the total amount of TAN in excreta deposited in and around buildings, and the total amount of TAN in manure (i.e. the excreta deposited in and around buildings after collection and storage) prior to spreading and were ca. 64-88 x 10(3) t. The NH3-N emission from livestock buildings and manure storage in E&W quoted in the UK Emission Inventory (Pain et al., 1999. Inventory of Ammonia Emission from UK Agriculture, 1977. Report of MAFF contract WAO630, IGER, North Wyke) is ca. 80 x 10(3) t. Losses from NO3- leaching in the season after manure application and grazing were estimated as 73 and 32 x 10(3) t, respectively. Other gaseous losses of N were estimated as ca. 54 x 10(3) t. Crop uptake of manure N was estimated to be between 7 and 24 x 10(3) t. For manures, estimated N losses, immobilization and crop uptake total 326 x 10(3) t compared with estimates of 293-319 x 10(3) t TAN in excreta. Total N losses and crop uptake from TAN deposited at grazing were estimated to be 179-199 x 10(3) t compared with ca. 224 x 10(3) t TAN excreted. Thus all the TAN in manures appears to be accounted for, but ca. 25-45 x 10(3) t of TAN in urine deposited at grazing were not, and could be an underestimated source of gaseous emission or nitrate leaching.     

Unregulated greenhouse gas and ammonia emissions from current technology heavy-duty vehicles

The study presents the measurement of carbonyl, BTEX (benzene, toluene, ethyl benzene, and xylene), ammonia, elemental/organic carbon (EC/OC), and greenhouse gas emissions from modern heavy-duty diesel and natural gas vehicles. Vehicles from different vocations that included goods movement, refuse trucks, and transit buses were tested on driving cycles representative of their duty cycle. The natural gas vehicle technologies included the stoichiometric engine platform equipped with a three-way catalyst and a diesel-like dual-fuel high-pressure direct-injection technology equipped with a diesel particulate filter (DPF) and a selective catalytic reduction (SCR). The diesel vehicles were equipped with a DPF and SCR. Results of the study show that the BTEX emissions were below detection limits for both diesel and natural gas vehicles, while carbonyl emissions were observed during cold start and low-temperature operations of the natural gas vehicles. Ammonia emissions of about 1 g/mile were observed from the stoichiometric natural gas vehicles equipped with TWC over all the driving cycles. The tailpipe GWP of the stoichiometric natural gas goods movement application was 7% lower than DPF and SCR equipped diesel. In the case of a refuse truck application the stoichiometric natural gas engine exhibited 22% lower GWP than a diesel vehicle. Tailpipe methane emissions contribute to less than 6% of the total GHG emissions.

Implications: Modern heavy-duty diesel and natural gas engines are equipped with multiple after-treatment systems and complex control strategies aimed at meeting both the performance standards for the end user and meeting stringent U.S. Environmental Protection Agency (EPA) emissions regulation. Compared to older technology diesel and natural gas engines, modern engines and after-treatment technology have reduced unregulated emissions to levels close to detection limits. However, brief periods of inefficiencies related to low exhaust thermal energy have been shown to increase both carbonyl and nitrous oxide emissions.