Ozone Weekend Effect Analysis in Three European Urban Areas

This paper aims to apply statistical procedures to analyse the ozone weekend effect (OWE) in three European urban areas: Lisbon, Oporto and London. Seasonal variations of surface ozone (O₃) and total oxidant species (O_x) concentrations are presented. The studied period was from January 2007 to December 2009. The O₃ annual average profile in London was significantly different from the ones achieved for Lisbon and Oporto, due to the high emissions of nitrogen oxides and low temperatures (associated with low solar radiations). The influence of nitrogen oxides in atmospheric chemistry of London was analysed by linear correlations between O₃ concentrations and NO₂/NO ratio. High values during almost all period showed that O₃ concentrations are mainly influenced by NO? NO₂? O₃ chemical reaction. On the other hand, the linear correlations between O₃ and NO₂ concentrations only presented positive values in Lisbon and Oporto. This behaviour is associated with photo‐dissociation of NO₂, producing O₃ during the spring and summer periods. Additionally, cluster analysis was applied to group the days of week according the correspondent O₃ behaviour. The weekend and some weekdays (immediately after or before) were grouped in the same cluster, showing that OWE occurs in all urban areas selected in this study. These findings suggest that the applied statistical procedures should be used to analyse the OWE and that the causes for the different O₃ behaviours during the week may be influenced by meteorological variables.     

Investigating Correlations and Variations of Air Pollutant Concentrations under Conditions of Rapid Industrialization – Kocaeli (1987–2009)

In this study, it was aimed to characterize temporal variations of air pollutants for determining contribution to pollution episodes and to obtain correlations between these pollutants. With this aim we used data analysis for measured sulfur dioxide (SO₂), particulate matter (PM, black fume and PM10), nitrogen oxides (NO_x), ozone (O₃), carbon monoxide (CO), methane (CH₄), and non‐methane hydrocarbons (NMHC) recorded in Kocaeli, one of the most industrilizated cities of Turkey. Pollutant concentrations were the results of continuous and semi‐automatic measurements. Semi‐automatic measurements of SO₂ and PM (black fume) were enclosing period from 1987 to 2008 whereas continuous monitoring of all pollutants included years of 2007–2009. In the first stage of the study daily, monthly, annual, and seasonal variations of pollution were researched. Annual average concentrations were compared with limits set by Air Quality Protection Regulation (AQPR), Air Quality Evaluation and Management Regulation (AQEMR), World Health Organization (WHO), European Union (EU), and National Ambient Air Quality Standards (USEPA). In the following stage relationships between pollutants such as NO₂–O₃, NO_x–CO, NO_x–NMHC, and NO_x–SO₂ were investigated and correlation coefficients were determined as 0.87, 0.56, 0.51, and 0.69, respectively. R² values of regression models developed from these correlations were 0.78, 0.56, 0.34, and 0.72, respectively. Vehicle density of the traffic was evaluated with NO_x–O₃ emissions and decrease was seen in NO_x emissions due to decreasing vehicle density at weekends whereas O₃ concentrations increased. These correlations enable prediction of the parameters that cannot be measured which is important for providing improvement in early warning systems.     

Response of surface water chemistry to reduced levels of acid precipitation: comparison of trends in two regions of New York,USA

In light of recent reductions in sulphur (S) and nitrogen (N) emissions mandated by Title IV of the Clean Air Act Amendments of 1990, temporal trends and trend coherence in precipitation (1984–2001 and 1992–2001) and surface water chemistry (1992–2001) were determined in two of the most acid‐sensitive regions of North America, i.e. the Catskill and Adirondack Mountains of New York. Precipitation chemistry data from six sites located near these regions showed decreasing sulphate (SO₄^2?), nitrate (NO₃^?), and base cation (C_B) concentrations and increasing pH during 1984–2001, but few significant trends during 1992–2001. Data from five Catskill streams and 12 Adirondack lakes showed decreasing trends in SO₄^2? concentrations at all sites, and decreasing trends in NO₃^?, C_B, and H⁺ concentrations and increasing trends in dissolved organic carbon at most sites. In contrast, acid‐neutralizing capacity (ANC) increased significantly at only about half the Adirondack lakes and in one of the Catskill streams. Flow correction prior to trend analysis did not change any trend directions and had little effect on SO₄^2? trends, but it caused several significant non‐flow‐corrected trends in NO₃^? and ANC to become non‐significant, suggesting that trend results for flow‐sensitive constituents are affected by flow‐related climate variation. SO₄^2? concentrations showed high temporal coherence in precipitation, surface waters, and in precipitation–surface water comparisons, reflecting a strong link between S emissions, precipitation SO₄^2? concentrations, and the processes that affect S cycling within these regions. NO₃^? and H⁺ concentrations and ANC generally showed weak coherence, especially in surface waters and in precipitation–surface water comparisons, indicating that variation in local‐scale processes driven by factors such as climate are affecting trends in acid–base chemistry in these two regions. Copyright © 2005 John Wiley & Sons, Ltd.     

Influences of catchment characteristics on nitrogen concentration in largely forested streams during the base flow period

Based on measured stream nitrogen concentrations at outlets of 12 small sub‐areas (1·3–54·7 km²) in a largely forested catchment during the base flow period, we investigated the influences of discharges and different catchment characteristics on stream nitrogen concentration. Our field surveys were carried out during the 11‐month's period from April 2001 to February 2002 and the correlations between nitrogen concentrations and catchment characteristics were studied. The results showed that the vegetation cover was strongly correlated to total nitrogen (TN) and nitrate + nitrite ? nitrogen (NO_x‐N) concentrations. That is, the TN and NO_x‐N concentrations had positive correlations with mean normalized difference vegetation cover index (NDVI) of each sub‐area during dormant seasons (mean NDVI < 0 · 70) and had negative correlations during the growing season (mean NDVI ≥ 0 . 70). The significance of catchment characteristics to TN and NO_x‐N concentrations was ranked as vegetation cover > soil > topography > land use, and the best models can account for 55–64% of the variance of TN and NO_x‐N concentrations. Copyright © 2006 John Wiley & Sons, Ltd.     

Variations in trace gas concentrations in different environments in India

Observations of trace gases (SO₂, NH₃, NO₂ and O₃) were made during the period 1981 to 1984 at 6 different locations representative of urban industrial, urban, nonurban, thermal power plant and marine environment. Diurnal variations of the trace gases were studied in an urban environment. Except in the urban industrial environment, the concentration of NH₃ was found in the range of background values. Also, the average concentrations of NO₂ and O₃ at the different environments were in the order of background values. However, the concentrations of SO₂ were substantially higher by about 7 times, in urban industrial and thermal power plant environments. The diurnal variations of SO₂, NH₃ and NO₂ showed anitphase relationship with surface temperature at the urban environment station which is relatively free of industrial pollution. Discussion is centred on trace gas variations in different environments in India together with the values reported for various countries in the world.     

Using hydrochemical tracers to assess impacts of unsewered urban catchments on hydrochemistry and nutrients in groundwater

We applied graphical methods and multivariate statistics to understand impacts of an unsewered slum catchment on nutrients and hydrochemistry of groundwater in Kampala, Uganda. Data were collected from 56 springs (groundwater), 22 surface water sites and 13 rain samples. Groundwater was acidic and dominated by Na, Cl and NO₃. These ions were strongly correlated, indicating pollution originating from wastewater infiltration from on‐site sanitation systems. Results also showed that rain, which was acidic, impacted on groundwater chemistry. Using Q‐mode hierarchical cluster analysis, we identified three distinct water quality groups. The first group had springs dominated by Ca‐Cl‐NO₃, low values of electrical conductivity (EC), pH and cations, and relatively high NO₃ values. These springs were shown to have originated from the acidic rains because their chemistry closely corresponded to ion concentrations that would occur from rainfall recharge, which was around 3.3 times concentrated by evaporation. The second group had springs dominated by Na‐K‐Cl‐NO₃ and Ca‐Cl‐NO₃, low pH but with higher values of EC, NO₃ and cations. We interpreted these as groundwater affected by both acid rain and infiltration of wastewater from urban areas. The third group had the highest EC values (average of 688 μS/cm), low pH and very high concentrations of NO₃ (average of 2.15 mmol/l) and cations. Since these springs were all located in slum areas, we interpreted them as groundwater affected by infiltration of wastewater from poorly sanitized slums areas. Surface water was slightly reducing and eutrophic because of wastewater effluents, but the contribution of groundwater to nutrients in surface water was minimal because o‐PO₄ was absent, whereas NO₃ was lost by denitification. Our findings suggest that groundwater chemistry in the catchment is strongly influenced by anthropogenic inputs derived from nitrogen‐containing rains and domestic wastewater. Copyright © 2013 John Wiley & Sons, Ltd.     

Instantaneous global ozone balance including observed nitrogen dioxide

The catalytic destruction of stratospheric ozone by the oxides of nitrogen is believed to be an important part of the global ozone balance. The lack of sufficient measurements of NO _x concentrations has impeded efforts to quantify this process. Recent measurements of stratospheric nitrogen dioxide from ground-based stations as well as aircraft and balloons have provided a first approximation to a global distribution of NO₂ vertical columns at sunset. These observed vertical columns have been translated into time-dependent vertical NO₂ profiles by means of a one-dimensional atmospheric photochemical model. Using recent observations of air temperature and ozone along with this information, the independent instantaneous (one second) rates of ozone production from oxygen photolysis P(O₃), of ozone destruction from pure oxygen species (Chapman reactions) L(O _x ), and of ozone destruction by nitrogen oxides L(NO _x ) were estimated over the three-dimensional atmosphere. These quantities are displayed as zonal average contour maps, summed over various latitude zones, summed over various altitude bands, and integrated globally between 15 and 45 km. Although the global summation between 15 and 45 km by no means tells the complete story, these numbers are of some interest, and the relative values are: P(O₃), 100; L(O _x ), 15; L(NO _x ), 45±15. It is to be emphasized that this relative NO _x contribution to the integrated ozone balance is not a measure of the sensitivity of ozone to possible perturbations of stratospheric NO _x ; recent model results must be examined for current estimates of this sensitivity.     

The atmospheric effects of October 2003 solar proton event simulated with the chemistry–climate model SOCOL using complete and parameterized ion chemistry

October 2003 solar proton events (SPE) is rather well covered by the observations; therefore its studies represent a good way for model validation and intercomparison. Here we apply chemistry–climate model (CCM) SOCOL with complete (SOCOLⁱ) and parameterized ion chemistry to evaluate the accuracy of a commonly used ion chemistry parameterization scheme. We performed ensemble experiments with and without SPE to characterize the effect of the October 2003 SPE on the NO_x, HO_x, ClO_x and O₃ in the middle atmosphere. Preliminary comparison of the simulated effects against MIPAS observations revealed rather good general agreement for most of the species. Comparison of the results obtained with complete and parameterized ion chemistry representation showed that the model with parameterized ion chemistry underestimates the effect of SPE on chemical composition of the middle atmosphere by up to 40% for NO_x and N₂O, up to 70% for HO_x and ClO_x and up to 600% for HNO₃. The parameterization is more accurate for ozone, however the model with parameterized ion chemistry underestimates ozone depletion by up to 15% during the SPE in the mesosphere and by 10% 2 weeks later in the stratosphere, which can be important for the long-term effects of SPE on the ozone layer.     

The present-day and future impact of NOx emissions from subsonic aircraft on the atmosphere in relation to the impact of NOx surface sources

The effect of present-day and future NO_x emissions from aircraft on the NO_x and ozone concentrations in the atmosphere and the corresponding radiative forcing were studied using a three-dimensional chemistry transport model (CTM) and a radiative model. The effects of the aircraft emissions were compared with the effects of the three most important anthropogenic NO_x surface sources: road traffic, electricity generation and industrial combustion. From the model results, NO_x emissions from aircraft are seen to cause an increase in the NO_x and ozone concentrations in the upper troposphere and lower stratosphere, and a positive radiative forcing. For the reference year 1990, the aircraft emissions result in an increase in the NO_x concentration at 250 hPa of about 20 ppt in January and 50 ppt in July over the eastern USA, the North Atlantic Flight Corridor and Western Europe, corresponding to a relative increase of about 50%. The maximum increase in the ozone concentrations due to the aircraft emissions is about 3-4 ppb in July over the northern mid-latitudes, corresponding to a relative increase of about 3-4%. The aircraft-induced ozone changes cause a global average radiative forcing of 0.025 W/m² in July. According to the ANCAT projection for the year 2015, the aircraft NO_x emissions in that year will be 90% higher than in the year 1990. As a consequence of this, the calculated NO_x perturbation by aircraft emissions increases by about 90% between 1990 and 2015, and the ozone perturbation by about 50-70%. The global average radiative forcing due to the aircraft-induced ozone changes increases by about 50% between 1990 and 2015. In the year 2015, the effects of the aircraft emissions on the ozone burden and radiative forcing are clearly larger than the individual effects of the NO_x surface sources. Taking chemical conversion in the aircraft plume into account in the CTM explicitly, by means of modified aircraft NO_x emissions, a significant reduction of the aircraft-induced NO_x and ozone perturbations is realised. The NO_x perturbation decreases by about 40% and the ozone perturbation by about 30% in July over Western Europe, the eastern USA and the North Atlantic Flight Corridor.     

The controls on boreal peatland surface water chemistry in Northern Alberta,Canada

Spatial and temporal variability in surface water chemistry, organic soil chemistry and hydrologic indicators were investigated at three poor‐fen complexes in two boreal catchments in Northern Alberta to provide insight into the dominant controls on surface water chemistry. Improved understanding of these controls is required to enable prediction of runoff chemistry in the region under changing atmospheric deposition conditions. Surface water chemistry exhibited considerable variability; within each fen conductivity, dissolved organic carbon (DOC), and Cl⁻ tended to decrease and pH tended to increase with increasing distance from the lake edge. Variations in evaporative isotopic enrichment in ²H and ¹⁸O, expressed as deuterium excess, were used to distinguish between throughflow waters and those that were more evaporatively enriched. Throughflow surface waters were more acidic primarily due to higher concentrations of DOC and NO₃⁻. Exchangeable base saturation and pH of organic soils were strongly related to surface water chemistry at two of the fen complexes, demonstrating the capacity for cation exchange to influence surface water chemistry. Fen surface water concentrations of most elements and DOC increased during the summer period (between June and August), while pH of water decreased. Evaporative concentration of the surface waters was a dominant driver, with surface water temperature increasing at both catchments. Localized groundwater discharge was an important contributor of base cations to the fens, while the organic soils are sinks for atmospherically deposited SO₄²⁻, N and Cl⁻. Copyright © 2010 John Wiley & Sons, Ltd.     

Groundwater flushing of solutes at wetland and hillslope positions during storm events in a small glaciated catchment in western New York,USA

While the role of groundwater in flushing of solutes has long been recognized, few studies have explicitly studied the within‐event changes in groundwater chemistry. We compared the changes in groundwater chemistry during storm events for a wetland and hillslope position in a small (1·5 ha) glaciated, forested catchment in western New York. Flushing responses for dissolved organic carbon (DOC) and nitrogen (DON), nitrate (NO₃) and sulfate (SO₄) in wetland and hillslope groundwaters were also compared against the corresponding responses in stream water. Eight storm events with varying intensity, amount, and antecedent moisture conditions were evaluated. Solute flushing patterns for wetland and hillslope groundwaters differed dramatically. While DOC concentrations in wetland groundwater followed a dilution trend, corresponding values for hillslope groundwater showed a slight increase. Concentrations for NO₃ in wetland groundwater were below detection limits, but hillslope groundwaters displayed high NO₃ concentrations with a pronounced increase during storm events. Flushing responses at all positions were also influenced by the size of the event and the time between events. We attributed the differences in flushing to the differences in hydrologic flow paths and biogeochemical conditions. Flushing of the wetland did appear to influence storm‐event stream chemistry but the same could not be said for hillslope groundwaters. This suggests that while a variety of flushing responses may be observed in a catchment, only a subset of these responses affect the discharge chemistry at the catchment outlet. Copyright © 2009 John Wiley & Sons, Ltd.     

Spatial and temporal variations of nutrient concentration in the groundwater of a floodplain: effect of hydrology,vegetation and substrate

Spatio‐temporal variations in nitrogen and phosphorus concentrations in groundwater were analysed and related to the variations in hydrological conditions, vegetation type and substrate in an alluvial ecosystem. This study was conducted in the Illwald forest in the Rhine Plain (eastern France) to assess the removal of nutrients from groundwater in a regularly flooded area. We compared both forest and meadow ecosystems on clayey‐silty soils with an anoxic horizon (pseudogley) at 1·5–2 m depth (eutric gley soil) and a forest ecosystem on a clayey‐silty fluviosoil rich in organic matter with a gley at 0·5 m depth (calcaric gley soil). Piezometers were used to measure the nutrient concentrations in the groundwater at 2 m depth in the root layer and at 4·5 m depth, below the root layer. Lower concentrations of nitrate and phosphate in groundwater were observed under forest than under meadow, which could be explained by more efficient plant uptake by woody species than herbaceous plants. Thus NO₃‐N inputs by river floods were reduced by 73% in the shallow groundwater of the forested ecosystem, and only by 37% in the meadow. Compared with the superficial groundwater layer, the lowest level of nitrate nitrogen (NO₃‐N) and the highest level of ammonium nitrogen (NH₄‐N) were measured in the deep layer (under the gley horizon at 2·5 m depth), which suggests that the reducing potential of the anoxic horizon in the gley soils contributes to the reduction of nitrate. Nitrate concentrations were higher in the groundwater of the parcel rich in organic matter than in the one poorer in organic matter. Phosphate (PO₄‐P) concentrations in both shallow and deep groundwater are less than 62 to 76% of those found in surface water which can be related to the retention capacity of the clay colloids of these soils. Moreover, the temporal variations in nutrient concentrations in groundwater are directly related to variations in groundwater level during an annual hydrological cycle. Our results suggest that variations in groundwater level regulate spatio‐temporal variations in nutrient concentrations in groundwater as a result of the oxidation–reduction status of soil, which creates favourable or unfavourable conditions for nutrient bioavailability. The hydrological variations are much more important than those concerning substrate and type of vegetation. Copyright © 1999 John Wiley & Sons, Ltd.     

Spatial Distribution of SO2, NO2, and O3 Concentrations in an Industrial City of Turkey Using a Passive Sampling Method

Ambient concentrations of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and ozone (O₃) were measured at 51 sampling points by passive sampling technique in Kocaeli, an important industrial city in Turkey. Samples were analyzed by UV‐spectrophotometry for NO₂ and O₃ and by ion chromatography for SO₂, respectively. Concentrations of SO₂, NO₂, and O₃ were determined to investigate their spatial distribution and source characterization. The sampling campaigns revealed an average concentration of 8 µg/m³ (max. 82 µg/m³) for SO₂, and 14 µg/m³ (max. 40 µg/m³) for NO₂, in summer; while average winter concentrations were 25 µg/m³ (max. 61 µg/m³) for SO₂, and 50 µg/m³ (max. 100 µg/m³) for NO₂. The maximum ozone concentrations were determined to be 86 µg/m³ in summer and 61 µg/m³ in winter downwind of the source areas of the precursor pollutant emissions. The results showed that NO₂ and SO₂ concentrations in industrial and urban areas were two to four times higher compared with rural areas in the summer and winter. In the light of the information obtained from the spatial interpolation of the pollutant concentrations, a selection of appropriate locations for continuous monitoring was suggested according to the European Community (EU) directives.     

Analysis of Summer Ozone Observations at a High Mountain Site in Central Italy (Campo Imperatore, 2388 m a.s.l.)

Tropospheric ozone (O₃) is an important atmospheric pollutant and climate forcer. The Mediterranean basin is a hot-spot region in terms of short-term O₃ distribution, with frequent episodes of high tropospheric O₃, especially during summer. To improve the characterisation of summer O₃ variability in the Mediterranean area, during the period 6–27 August 2009 an experimental campaign was conducted at Campo Imperatore, Mt Portella (CMP), a high mountain site (2,388 m a.s.l.) located in the central Italian Apennines. As deduced from analysis of atmospheric circulation, the measurement site was significantly affected by air masses originating over the Mediterranean basin, which affected the measurement site for 32 % of the time. Analysis of average values and diurnal and day-to-day variability revealed that CMP O₃ observations (average value 60.0 ± 5.1 ppbv) were comparable with measurements at other European mountain stations, indicating a prevalent effect of meteorological conditions and atmospheric transport on the synoptic scale. In fact, only a small “reverse” diurnal variation typically characterises diurnal O₃ variability because of local thermal wind circulation, which sporadically favours transport of air masses rich in O₃ from the foothill regions. Statistical analysis of five-day back-trajectory ensembles indicates that synoptic-scale air-mass transport from the Mediterranean Sea usually results in decreasing O₃ concentrations at CMP, whereas the highest hourly O₃ values are mostly associated with air masses from central continental Europe, eastern Europe, and northern Italy. High O₃ concentrations are also related to downward air-mass transport from higher altitudes. Comparison of in-situ O₃ variability with tropospheric O₃ satellite-based measurements reveals similar features of the two data sets. Together with the results from back-trajectory analysis, this indicates that CMP measurements might usefully improve characterisation of broad-scale O₃ variability over the central Mediterranean basin.     

Variable nitrate concentration–discharge relationships in a forested watershed

The relationship between solute concentrations and discharge can inform an integrated understanding of hydrological and biogeochemical processes at watershed scales. Recent work from multiple catchments has shown that there is typically little variation in concentration relative to large variations in discharge. This pattern has been described as chemostatic behavior. Pond Branch, a forested headwater catchment in Maryland, has been monitored for stream nitrate (NO₃^?) concentrations at weekly intervals for 14 years. In the growing season and autumn of 2011 a high‐frequency optical NO₃^? sensor was used to supplement the long‐term weekly data. In this watershed, long‐term weekly data show that NO₃^? concentrations decrease with increasing discharge whereas 6 months of 15‐minute sensor observed concentrations reveal a more chemostatic behavior. High‐frequency NO₃^? concentrations from the sensor collected during different storm events reveal variable concentration–discharge patterns highlighting the importance of high resolution data and ecohydrological drivers in controlling solute export for biologically reactive solutes such as NO₃^?.     

A theoretical interpretation of ion composition measured on board the ‘Active’ satellite in the European sector during April 10-12, 1990 geomagnetic storm

Ion composition measurements on board the ACTIVE satellite during the recovery phase of a strong geomagnetic storm of 10–12 April 1990 revealed extremely high concentrations (up to 10³ cm⁻³) of the NO⁺, O⁺₂, N⁺₂ molecular ions in the topside F2-region of the European high-latitude zone. Concentrations of O⁺, N⁺, He⁺, H⁺ light ions were slightly decreased relative to prestorm quite conditions. Theoretical calculations were used to analyze the observed variations in ion concentration. Increased neutral temperature and [O₂], [N₂] are shown to be the main reasons for the observed ion concentration variations.     

A discussion of the chemistry of some minor constituents in the stratosphere and troposphere

A discussion is given of atmospheric reactions in the H₂O–CH₄–O₂–O₃–NO _x system. In the lower troposphere such reactions may lead to significant production of ozone. Their role in the odd hydrogen balance, especially of the troposphere and lower stratosphere, is discussed. CH₃OH may be an intermediate in the oxidation cycle of methane, especially in the cold stratosphere. Its photodissociation into H₂ and CH₂O may consequently provide an important source for stratospheric H₂. Catalytic photochemical chains of reactions involving NO _x and HO _x may also lead to tropospheric destruction of ozone. Due to lack of knowledge it is not possible at present to evaluate the importance of the before-mentioned reactions.With the aid of model calculations it is indicated that stratospheric ozone is most sensitive to changes in the adopted lower boundary values of N₂O and that an increase in water vapour concentrations in the lower stratosphere will indeed cause some increase in ozone as predicted.Fluctuations in the flux of solar radiation near 190 nm may cause significant variations in stratospheric ozone concentrations.     

Impact of different energies of precipitating particles on NOx generation in the middle and upper atmosphere during geomagnetic storms

Energetic particle precipitation couples the solar wind to the Earth's atmosphere and indirectly to Earth's climate. Ionisation and dissociation increases, due to particle precipitation, create odd nitrogen (NO_x) and odd hydrogen (HO_X) in the upper atmosphere, which can affect ozone chemistry. The long-lived NO_x can be transported downwards into the stratosphere, particularly during the polar winter. Thus, the impact of NO_x is determined by both the initial ionisation production, which is a function of the particle flux and energy spectrum, as well as transport rates. In this paper, we use the Sodankylä Ion and Neurtal Chemistry (SIC) model to simulate the production of NO_x from examples of the most representative particle flux and energy spectra available today of solar proton events (SPE), auroral energy electrons, and relativistic electron precipitation (REP). Large SPEs are found to produce higher initial NO_x concentrations than long-lived REP events, which themselves produce higher initial NO_x levels than auroral electron precipitation. Only REP microburst events were found to be insignificant in terms of generating NO_x. We show that the Global Ozone Monitoring by Occultation of Stars (GOMOS) observations from the Arctic winter 2003–2004 are consistent with NO_x generation by a combination of SPE, auroral altitude precipitation, and long-lived REP events.     

Using Crater Lake chemistry to predict volcanic activity at Poás Volcano,Costa Rica

Monitoring of crater lake chemistry during the recent decline and disappearance of the crater lake of Poás Volcano revealed that large variations in SO₄/Cl, F/Cl, and Mg/Cl ratios were caused by the enhanced release of HCl vapor from the lake surface due to increasing lake temperature and solution acidity. Variation in the concentration of polythionic acids (H₂S_xO₆, x=4–6) was the most reliable predictor of renewed phreatic eruptive activity at the volcano, exhibiting sharp decreases three months prior to the initiation of phreatic eruptions in June 1987. Polythionic acids may offer a direct indicator of changing subsurface magmatic activity whereas chloride-based element ratios may be influenced by surface volatilization of HCl and subsequent recycling of acidic fluids in crater lake volcanoes.     

Nitrate dynamics in a rural headwater catchment: measurements and modelling

This study was designed to improve our understanding of, and mechanistically simulate, nitrate (NO₃) dynamics in a steep 9.8 ha rural headwater catchment, including its production in soil and delivery to a stream via surface and subsurface processes. A two‐dimensional modelling approach was evaluated for (1) integrating these processes at a hillslope scale annually and within storms, (2) estimating denitrification, and (3) running virtual experiments to generate insights and hypotheses about using trees in streamside management zones (SMZs) to mitigate NO₃ delivery to streams. Total flow was mathematically separated into quick‐ and slow‐flow components; the latter was routed through the HYDRUS software with a nitrogen module designed for constructed wetlands. Flow was monitored for two years. High surface‐soil NO₃ concentrations started to be delivered to the stream via preferential subsurface flow within two days of the storm commencing. Groundwater NO₃‐N concentrations decreased from 1.0 to less than 0.1 mg l^?1 from up‐slope to down‐slope water tables, respectively, which was attributed to denitrification. Measurements were consistent with the flushing of NO₃ mainly laterally from surface soil during and following each storm. The model accurately accounted for NO₃ turnover, leading to the hypotheses that denitrification was a minor flux (<3 kg N ha^?1) compared to uptake (98^?127 kg N ha^?1), and that SMZ trees would reduce denitrification if they lowered the water table. This research provides an example of the measurement and modelling of NO₃ dynamics at a small‐catchment scale with high spatial and temporal resolution. Copyright © 2013 John Wiley & Sons, Ltd.