Interactive effects of O3 exposure on California black oak (Quercus kelloggii Newb.) seedlings with and without N amendment

We examined the short-term separate and combined effects of simulated nitrogen (N) deposition (fertilization) and ozone (O(3)) exposure on California black oak seedlings (Quercus kelloggii Newb.), an ecologically important tree of the San Bernardino Mountains downwind of Los Angeles. Realistic concentrations of O(3) were found to cause statistically and biologically significant negative effects on plant health, including lowered photosynthetic ability, lowered water use efficiency, and increased leaf chlorosis and necrosis. When subjected to abrupt changes in light levels, O(3)-exposed plants showed both a slower and smaller response than O(3)-free plants. Fertilized plants exhibited a significantly greater pre- to post-treatment decline in A at saturated [CO(2)] and a significantly lower level of post-treatment chlorosis than unfertilized plants. Fertilization tended to reduce plant sensitivity to O(3).     

Sampling optimization, at site scale, in contamination monitoring with moss, pine and oak.

With the aim of optimizing protocols for sampling moss, pine and oak for biomonitoring of atmospheric contamination and also for inclusion in an Environmental Specimen Bank, 50 sampling units of each species were collected from the study area for individual analysis. Levels of Ca, Cu, Fe, Hg, Ni, and Zn in the plants were determined and the distributions of the concentrations studied. In moss samples, the concentrations of Cu, Ni and Zn, considered to be trace pollutants in this species, showed highly variable long-normal distributions; in pine and oak samples only Ni concentrations were log-normally distributed. In addition to analytical error, the two main source of error found to be associated with making a collective sample were: (1) not carrying out measurements on individual sampling units; and (2) the number of sampling units collected and the corresponding sources of variation (microspatial, age and interindividual). We recommend that a minimum of 30 sampling units are collected when contamination is suspected.     

The effect of nitrogen additions on oak foliage and herbivore communities at sites with high and low atmospheric pollution

To evaluate plant and herbivore responses to nitrogen we conducted a fertilization study at a low and high pollution site in the mixed conifer forests surrounding Los Angeles, California. Contrary to expectations, discriminant function analysis of oak herbivore communities showed significant response to N fertilization when atmospheric deposition was high, but not when atmospheric deposition was low. We hypothesize that longer-term fertilization treatments are needed at the low pollution site before foliar N nutrition increases sufficiently to affect herbivore communities. At the high pollution site, fertilization was also associated with increased catkin production and higher densities of a byturid beetle that feeds on the catkins of oak. Leaf nitrogen and nitrate were significantly higher at the high pollution site compared to the low pollution site. Foliar nitrate concentrations were positively correlated with abundance of sucking insects, leafrollers and plutellids in all three years of the study.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.     

Variations of surface O3 in August at a rural site near Shanghai: influences from the West Pacific subtropical high and anthropogenic emissions

Large day-to-day variability in O₃ and CO was observed at Chongming, a remote rural site east of Shanghai, in August 2010. High ozone periods (HOPs) that typically lasted for 3?C5?days with daily maximum ozone exceeding 102?ppb were intermittent with low ozone periods (LOPs) with daily maximum ozone less than 20?ppb. The correlation analysis of ozone with meteorological factors suggests that the large variations of surface ozone are driven by meteorological conditions correlated with the changes in the location and intensity of the west Pacific subtropical high (WPSH) associated with the East Asian summer monsoon (EASM). When the center of WPSH with weaker intensity is to the southeast of Chongming site, the mixing ratios and variability of surface ozone are higher. When the center of WPSH with stronger intensity is to the northeast of Chongming site, the mixing ratios and variability of surface ozone are lower. Sensitivity simulations using the GEOS-Chem chemical transport model indicate that meteorological condition associated with WPSH is the primary factor controlling surface ozone at Chongming in August, while local anthropogenic emissions make significant contributions to surface ozone concentrations only during HOP.     

Sulphur dioxide,oxides of nitrogen and ozone measured continuously for 2 years at a rural site

Continuous specific measurements of sulphur dioxide, nitric oxide, nitrogen dioxide and ozone have been made for over 2y at Bottesford, a rural site in central England, 20 km away from town and industry sources and 1 km from traffic sources. Statistics of hourly, daily, monthly, seasonal and yearly values are given.On an annual basis, there was 50% more oxides of nitrogen (nitric oxide plus nitrogen dioxide) than sulphur dioxide, and more ozone than either. The nitric oxide and nitrogen dioxide were approximately equal. No other published annual values of nitric oxide, nitrogen dioxide and ozone at U.K. rural sites are known. The summer nitric oxide values were greater at this site than at three other rural sites in the British Isles for which summer nitric oxide values have been reported, but so was the sulphur dioxide, and the amounts of both these gases probably reflect the size and distance of combustion sources.Diurnal variations of the four gases during summer months at Bottesford were similar to those published for a site in southern England. The diurnal variations for winter months at Bottesford were somewhat different, especially for nitrogen dioxide. No other published winter patterns are known.Usually nitrogen dioxide and ozone concentrations were in opposition, both short and long term, but on rare occasions, for example in relatively clean winter air, the ozone concentration rose and fell directly with the nitrogen dioxide. Hourly ozone values exceeded 50 ppb (10⁻⁹, by volume) for several hours a month in 22 months out of 24. The World Health Organisation guideline for public health exposure limits is given as 50–100 ppb h⁻¹, not to be exceeded more than once per month.     

The contribution of biological particles to observed particulate organic carbon at a remote high altitude site

Although a significant fraction of atmospheric particulate mass is organic carbon, the sources of particulate organic carbon (POC) are not always apparent. One potential source of atmospheric POC is biological particles, such as bacteria, pollen, and fungal spores. Measurements of POC and biological particles, including bacteria, fungal spores, and pollen, were made as part of the Storm Peak Aerosol and Cloud Characterization Study in Steamboat Springs, CO in March–April 2008. Biological particles were identified and characterized using several methods. The results suggest that biological particles could account for an average of 40% of the organic carbon mass in particles with aerodynamic diameters less than 10 μm. These estimates of POC mass from biological particles are highly uncertain; however, the results suggest that biological particles could be a significant source of organic aerosol in the background continental atmosphere and further observations are needed to better constrain these estimates.     

Atmospheric phase distribution of oxidized and reduced nitrogen at a forest ecosystem research site

Atmospheric concentrations of gaseous NH3 and HNO3 and of particulate NH4+ and NO3- were measured during various seasons at a forest ecosystem research site in the "Fichtelgebirge" mountains in Central Europe. Air masses arriving at this site were highly variable with respect to trace compound concentration levels and their concentration ratios. However, the distributions of NH4+ and NO3- within the aerosol particle size spectra exhibited some very consistent patterns, with the former dominating the fine particle concentrations, and the latter dominating the coarse particles range, respectively. Overall, the particulate phase (NH4+ + NO3-) dominated the atmospheric nitrogen budget (particulate and gas phase, NH4+ + NO3- + NH3 + HNO3) by more than 90% of the median total mixing ratio in winter, and by more than 60% in summer. The phase partitioning varied significantly between the winter and summer seasons, with higher relative importance of the gaseous species during summer, when air temperatures were higher and relative humidities lower as compared to the winter season. Reduced nitrogen dominated over oxidized nitrogen, indicating the prevailing influence of emissions from agricultural activity as compared to traffic emissions at this mountainous site. A model has been successfully applied in order to test the hypothesis of thermodynamic equilibrium between the particulate and gas phases.     

A cation exchange model to describe Cs+ sorption at high ionic strength in subsurface sediments at Hanford site, USA

A theoretical and experimental study of cation exchange in high ionic strength electrolytes was performed using pristine subsurface sediments from the U.S. Department of Energy Hanford site. These sediments are representative of the site contaminated sediments impacted by release of high level waste (HLW) solutions containing 137Cs+ in NaNO3 brine. The binary exchange behavior of Cs+-Na+, Cs+-K+, and Na+-K+ was measured over a range in electrolyte concentration. Vanselow selectivity coefficients (Kv) that were calculated from the experimental data using Pitzer model ion activity corrections for aqueous species showed monotonic increases with increasing electrolyte concentrations. The influence of electrolyte concentration was greater on the exchange of Na+-Cs+ than K+-Cs+, an observation consistent with the differences in ion hydration energy of the exchanging cations. A previously developed two-site ion exchange model [Geochimica et Cosmochimica Acta 66 (2002) 193] was modified to include solvent (water) activity changes in the exchanger phase through application of the Gibbs-Duhem equation. This water activity-corrected model well described the ionic strength effect on binary Cs+ exchange, and was extended to the ternary exchange system of Cs+-Na+-K+ on the pristine sediment. The model was also used to predict 137Cs+ distribution between sediment and aqueous phase (Kd) beneath a leaked HLW tank in Hanfordd's S-SX tank using the analytical aqueous data from the field and the binary ion exchange coefficients for the pristine sediment. The Kd predictions closely followed the trend in the field data and were improved by consideration of water activity effects that were considerable in certain regions of the vadose zone plume.     

Transport and fate of organic wastes in groundwater at the Stringfellow hazardous waste disposal site, southern California

In January 1999, wastewater influent and effluent from the pretreatment plant at the Stringfellow hazardous waste disposal site were sampled along with groundwater at six locations along the groundwater contaminant plume. The objectives of this sampling and study were to identify at the compound class level the unidentified 40-60% of wastewater organic contaminants, and to determine what organic compound classes were being removed by the wastewater pretreatment plant, and what organic compound classes persisted during subsurface waste migration. The unidentified organic wastes are primarily chlorinated aromatic sulfonic acids derived from wastes from DDT manufacture. Trace amounts of EDTA and NTA organic complexing agents were discovered along with carboxylate metabolites of the common alkylphenolpolyethoxylate plasticizers and nonionic surfactants. The wastewater pretreatment plant removed most of the aromatic chlorinated sulfonic acids that have hydrophobic neutral properties, but the p-chlorobenzene-sulfonic acid which is the primary waste constituent passed through the pretreatment plant and was discharged in the treated wastewaters transported to an industrial sewer. During migration in groundwater, p-chlorobenzenesulfonic acid is removed by natural remediation processes. Wastewater organic contaminants have decreased 3- to 45-fold in the groundwater from 1985 to 1999 as a result of site remediation and natural remediation processes. The chlorinated aromatic sulfonic acids with hydrophobic neutral properties persist and have migrated into groundwater that underlies the adjacent residential community.     

Cloudwater studies at a high elevation site in the Vosges Mountains (France)

Cloud and rainwater samples have been collected at a high elevation site in the Vosges Mountains. An automated collection system has been used to collect bulk cloudwater and small cloudwater droplets. Bulk cloudwater concentrations were up to 10 times more concentrated than rainwater concentrations. Small clouddroplets showed generally higher concentrations than bulk cloudwater. Nevertheless, the enrichment factors depend on the compounds under study and appear to be related to the composition of the cloud condensation nuclei forming small or large clouddroplets. Principal component analysis and factor analysis were applied to the collected datasets and confirmed the influence of the cloud condensation nuclei on the composition difference between small and large cloudwater droplets.     

Ten years of atmospheric methane observations at a high elevation site in Western China

In this paper, the continuous (1994–2001) and discrete air sample (1991–2001) measurements of atmospheric CH₄ from the Waliguan Baseline Observatory located in western China (36°17′N, 100°54′E, 3816 m asl) are presented and characterized. The CH₄ time series show large episodic events on the order of 100 ppb throughout the year. During spring, a diurnal cycle with average amplitude of 7 ppb and a morning maximum and late afternoon minimum is observed. In winter, a diurnal cycle with average amplitude of 14 ppb is observed with an afternoon maximum and morning minimum. Unlike most terrestrial observational sites, no obvious diurnal patterns are present during the summer or autumn. A background data selection procedure was developed based on local horizontal and vertical winds. A selected hourly data set representative of “baseline” conditions was derived with approximately 50% of the valid hourly data. The range of CH₄ mixing ratios, annual means, annual increases and mean annual cycle at Waliguan during the 1992–2001 were derived from discrete and continuous data representative of “baseline” conditions and compared to air samples collected at other Northern Hemisphere sites. The range of CH₄ monthly means of 1746–1822 ppb, average annual means of 1786.7±10.8 ppb and mean annual increase of 4.5±4.2 ppb yr⁻¹ at Waliguan were inline with measurements from sites located between 30° and 60°N. There were variations observed in the CH₄ annual increase patterns at Waliguan that were slightly different from the global pattern. The mean CH₄ annual cycle at Waliguan shows an unusual pattern of two gentle peaks in summer and February along with two small valleys in early winter and spring and a mean peak-to-peak amplitude of 11 ppb, much smaller than amplitudes observed at most other mid- and high-northern latitude sites. The Waliguan CH₄ data are strongly influenced by continental Asian CH₄ emissions and provide key information for global atmospheric CH₄ models.     

Tomato response to concurrent and sequential NO2 and O3 exposures

In the ambient environment, concentrations of air pollutants vary on a diurnal cycle, resulting in various patterns of concurrent and sequential exposures of plants. The response of tomato plants to sequential and concurrent NO2 and O3 exposures was determined using pollutant levels equal to the maximum acceptable levels recommended by the National Ambient Air Quality Objectives of Environment Canada for a 1 h average. The concurrent treatment, 1 h of NO2 + O3, was compared to 1 h of NO20, O3 or control in plants at the 4 to 6 or the 9 to 11 leaf stage. At the 4 to 6 leaf stage, leaf and stem fresh weights were significantly reduced by the NO2 + O3 treatment relative to control, whereas these growth parameters were not reduced relative to control by the single pollutants indicating a coalitive response. Leaf area was significantly smaller as a result of the NO2 + O3 treatment relative to the NO2 treatment. A main effect of O3 was observed on leaf dry weight. The sequential treatments were: NO2 followed by O3 (NO2-O3); O3 followed by NO2 (O3-NO2); NO2 at night followed by O3 during the daytime (NO2(N)-O3(D)). Each gas exposure was 1 h; only plants at the 4 to 6 leaf stage were treated. Only the O3-NO2 treatment significantly reduced leaf area, leaf fresh weight and stem fresh and dry weights relative to control plants. Inconsistencies among treatments occurring at different time periods of the day suggest that time period of exposure should reflect ambient time periods. The coalitive action, and the sequential treatment response, of these pollutants indicated that criteria based on single pollutants may not be adequate to establish air quality objectives when these pollutants occur together.     

Observations of particle growth at a remote,Arctic site

Observations of particle size distributions suggest that particles grow significantly just above the snow surface at a remote, Arctic site. Measurements were made at Summit, Greenland (71.38°N and 31.98°W) at approximately 3200 m above sea level. No new particle formation was observed locally, but growth of ultrafine particles was identified by continuous evolution of the geometric mean diameter (GMD) during four events. The duration of the growth during events was between 24 and 115 h, and calculated event-average growth rates (GR) were 0.09, 0.30, 0.27, and 0.18 nm h^?1 during each event, respectively. Four-hour GR up to 0.96 nm h^?1 were observed. Events occurred during below- and above-average temperatures and were independent of wind direction. Correlation analysis of hourly-calculated GR suggested that particle growth was limited by the availability of photochemically produced precursor gases. Sulfuric acid played a very minor role in particle growth, which was likely dominated by condensation of organic compounds, the source of which was presumably the snow surface. The role of boundary layer dynamics is not definite, although some mixing at the surface is necessary for the observation of particle growth. Due to the potentially large geographic extent of events, observations described here may provide a link between long-range transport of mid-latitude pollutants and climate regulation in the remote Arctic.     

Nitrification in polluted soil fertilized with fast- and slow-releasing nitrogen: a case study at a refinery landfarming site

The nitrifying activity and the effect of fertilization with urea and methylene urea were studied in a landfarming site. The site has been operative over 20 years and maintained by heavy nitrogen fertilization. The landfarming soil contained 4-6% (w/w) oil. The nitrate accumulation was 20-50mg NO3-N day(-1)kg(-1) observed after methylene urea fertilization of 889 g Nm(-2). Nitrification ex situ (in laboratory conditions) was 8.8 mg NO3-N day(-1) kg(-1) in the presence of 380 mg kg(-1) NH4+-N. The half-saturation concentration of nitrification was more than 200 mg NH4+-N kg(-1). The results show that nitrification was active in soil with high oil concentration. Urea fertilization of 893 g Nm(-2) caused an increase of soil NH4+-N concentration up to 5500 mg kg(-1) and pH>8.5. This led to inhibition of nitrification, which persisted after NH4+ concentration decreased below 200mg NH4+ kg(-1).     

Modelling acidification at Beacon Hill-a low rainfall, high pollutant deposition site in Central England

The model MAGIC (Model of Acidification of Groundwater In Catchments) has been applied to the Beacon Hill site, near Loughborough in Central England. This site is heavily impacted by wet and dry deposition of oxides of sulphur and nitrogen. The high acid inputs have caused soil acidification and acid stream waters. Long term simulations suggest that there has been a major decline in alkalinity and pH over the past 50 years. Despite recent reductions in deposition levels, soils and streams are predicted to continue to acidify in the future. For this heavily impacted site, deposition must be reduced by 80-90% to reverse the acidification trend and allow recovery of soil and stream waters.     

Open-path,closed-path,and reconstructed aerosol extinction at a rural site

The Handix Scientific open-path cavity ringdown spectrometer (OPCRDS) was deployed during summer 2016 in Great Smoky Mountains National Park (GRSM). Extinction coefficients from the relatively new OPCRDS and from a more well-established extinction instrument agreed to within 7%. Aerosol hygroscopic growth (f(RH)) was calculated from the ratio of ambient extinction measured by the OPCRDS to dry extinction measured by a closed-path extinction monitor (Aerodyne’s cavity-attenuated phase shift particulate matter extinction monitor [CAPS PMex]). Derived hygroscopicity (relative humidity [RH] < 95%) from this campaign agreed with data from 1995 at the same site and time of year, which is noteworthy given the decreasing trend for organics and sulfate in the eastern United States. However, maximum f(RH) values in 1995 were less than half as large as those recorded in 2016—possibly due to nephelometer truncation losses in 1995. Two hygroscopicity parameterizations were investigated using high-time-resolution OPCRDS+CAPS PMex data, and the κ_ext model was more accurate than the gamma model. Data from the two ambient optical instruments, the OPCRDS and the open-path nephelometer, generally agreed; however, significant discrepancies between ambient scattering and extinction were observed, apparently driven by a combination of hygroscopic growth effects, which tend to increase nephelometer truncation losses and decrease sensitivity to the wavelength difference between the two instruments as a function of particle size. There was not a statistically significant difference in the mean reconstructed extinction values obtained from the original and the revised IMPROVE (Interagency Monitoring of Protected Visual Environments) equations. On average, IMPROVE reconstructed extinction was ~25% lower than extinction measured by the OPCRDS, which suggests that the IMPROVE equations and 24-hr aerosol data are moderately successful in estimating current haze levels at GRSM. However, this conclusion is limited by the coarse temporal resolution and the low dynamic range of the IMPROVE reconstructed extinction.

Implications: Although light extinction, which is directly related to visibility, is not directly measured in U.S. National Parks, existing IMPROVE protocols can be used to accurately infer visibility for average humidity conditions, but during the large fraction of the year when humidity is above or below average, accuracy is reduced substantially. Furthermore, nephelometers, which are used to assess the accuracy of IMPROVE visibility estimates, may themselves be biased low when humidity is very high. Despite reductions in organic and sulfate particles since the 1990s, hygroscopicity, particles’ affinity for water, appears unchanged, although this conclusion is weakened by the previously mentioned nephelometer limitations.     

Concentrations of ammonia and nitrogen dioxide at roadside verges, and their contribution to nitrogen deposition

Bimonthly integrated measurements of NO2 and NH3 have been made over one year at distances up to 10 m away from the edges of roads across Scotland, using a stratified sampling scheme in terms of road traffic density and background N deposition. The rate of decrease in gas concentrations away from the edge of the roads was rapid, with concentrations falling by 90% within the first 10 m for NH3 and the first 15 m for NO2. The longer transport distance for NO2 reflects the production of secondary NO2 from reaction of emitted NO and O3. Concentrations above the background, estimated at the edge of the traffic lane, were linearly proportional to traffic density for NH3 (microg NH3 m(-3) = 1 x 10(-4) x numbers of cars per day), reflecting emissions from three-way catalysts. For NO2, where emissions depend strongly on vehicle type and fuel, traffic density was calculated in terms of 'car equivalents'; NO2 concentrations at the edge of the traffic lane were proportional to the number of car equivalents (microg NO2 m(-3) = 1 x 10(-4) x numbers of car equivalents per day). Although absolute concentrations (microg m(-3)) of NH3 were five times smaller than for NO2, the greater deposition velocity for NH3 to vegetation means that approximately equivalent amounts of dry N deposition to road side vegetation from vehicle emissions comes from NH3 and NO2. Depending on traffic density, the additional N deposition attributable to vehicle exhaust gases is between 1 and 15 kg N ha(-1) y(-1) at the edge of the vehicle lane, falling to 0.2-10 kg N ha(-1) y(-1) at 10 m from the edge of the road.     

Trends and Relationships of O3, NOx and HC in the South Coast Air Basin of California

A basin-wide air quality trend analysis for the South Coast Air Basin of California is conducted for hydrocarbons (HC), NO_x, O₃ and CO using multi-station composite daily maximum-hour average ambient concentrations for the third quarter (July, August and September) from 1968 to 1985. Emissions and air quality trends are compared for the period 1968-1984. Ambient HC and NOX trends are somewhat different from estimated emission trends of HC and NO_x, while a definite, downward trend of ambient CO is consistent with vehicular emission control measures. Basin-wide ambient HC, NO_x and O₃ appear to show downward trends for the period 1970-1985, but because of high fluctuations it is difficult to delineate trends for shorter periods. The meteorology (850 mb temperature)-adjusted O₃ shows a more consistent downward trend than does unadjusted O₃. Polynomial and multiplicative regression models for basin-wide empirical O₃-HC-NO_x relationships Indicate that the O₃ variation is explained largely by the meteorological variable (850 mb temperature) although model estimations are improved by adding HC and NO_x concentration terms.