Hydroxyl (OH) radical production rates in snowpacks from photolysis of hydrogen peroxide (H2O2) and nitrate (NO3−)

Atmospheric chemistry directly above snowpacks is strongly influenced by ultraviolet (UV) radiation initiated emissions of chemicals from the snowpack. The emission of gases from the snowpack to the atmosphere is in part due to chemical reactions between hydroxyl radical, OH (produced from photolysis of hydrogen peroxide (H₂O₂) or nitrate (NO₃⁻)) and impurities in the snowpack. The work presented here is a radiative-transfer modelling study to calculate the depth-integrated production rates of hydroxyl radical from the photolysis of hydrogen peroxide and nitrate anion in snow for four different snowpacks and for solar zenith angles 30°–90°. This work also demonstrates the importance of hydrogen peroxide photolysis to produce hydroxyl radical relative to nitrate photolysis with (a) different snowpacks, (b) different ozone column depths, and (c) snowpack depths. The importance of hydrogen peroxide photolysis over nitrate photolysis for hydroxyl radical production increases with increasing depth in snowpack, column ozone depth, and solar zenith angle. With a solar zenith angle of 60° the production of hydroxyl radical from hydrogen peroxide photolysis accounts for 91–99% of all hydroxyl radical production from hydrogen peroxide and nitrate photolysis.     

Estimation of night-time N2O5 concentrations from ambient NO2 and NO3 radical concentrations and the role of N2O5 in night-time chemistry

Dinitrogen pentoxide (N₂O₅), which is present in equilibrium with NO₃ radicals and NO₂, has been recognized for some time as an intermediate in the NO_x chemistry of night-time atmospheres. However, until the advent of long pathlength spectroscopic techniques for the measurement of atmospheric NO₃ radical concentrations, no reliable method for estimating N₂O₅ concentrations has been available. We have calculated maximum night-time N₂O₅ concentrations from the available experimentally determined concentrations of the NO₃ radical and NO₂ in the U.S. and Germany, and find that N₂O₅ concentrations as high as ~ 15 ppb can occur. We have also estimated removal rates for N₂O₅ and for NO₃ radicals during these nights. From data obtained under conditions devoid of point sources of NO_x, upper limit estimates of the homogeneous rate constant for the reaction of N₂O₅ with water vapor are obtained, leading to the conclusion that the homogeneous gas phase rate constant for this reaction is ⩽ 1 × 10⁻²¹ cm³ molecule⁻¹ s⁻¹ at 298 K, consistent with recent environmental chamber data.     

Measures of ozone concentrations using passive sampling in forests of South Western Europe

Ambient ozone concentrations were measured with passive samplers in the framework of the EU and UN/ECE Level II forest monitoring programme. Data from France, Italy, Luxembourg, Spain and Switzerland are reported for 2000-2002, covering the period from April to September. The number of plots increased from 67 in 2000 to 83 in 2002. The year 2001 experienced the highest ozone concentrations, reflecting more stable summer meteorological conditions. Average 6-month ozone concentrations above 45 ppb were measured this year in 40.3% of the plots, in contrast with the less than 21% measured in the other 2 years. Gradients of increasing ozone levels were observed from North to South and with altitude. Comments are made on the regional trends and on the time frame of the higher ozone episodes. Also, some recommendations enabling a better comparison between plots are provided.     

Recovery of the histogram of hourly ozone distribution from weekly average concentrations

A simple method is presented for estimating hourly distribution of air pollutants, based on data collected by passive sensors on a weekly or bi-weekly basis with no need for previous measurements at a site. In order for this method to be applied to locations where no hourly records are available, reference data from other sites are required to generate calibration histograms. The proposed procedure allows one to obtain the histogram of hourly ozone values during a given week with an error of about 30%, which is good considering the simplicity of this approach. This method can be a valuable tool for sites that lack previous hourly records of pollutant ambient concentrations, where it can be used to verify compliance with regulations or to estimate the AOT40 index with an acceptable degree of exactitude.     

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Because investigations of PAN at higher southern latitudes are very scarce, we measured surface PAN concentrations for the first time in Antarctica. During the Photochemical Experiment at Neumayer (PEAN'99) campaign mean surface PAN mixing ratios of 13±7 pptv and maximum values of 48 pptv were found. When these PAN mixing ratios were compared to the sum of NO_x and inorganic nitrate they were found to be equal or higher. Low ambient air temperatures and low PAN concentrations caused a slow homogeneous PAN decomposition rate of approximately 5×10⁻² pptv h⁻¹. These slow decay rates were not sufficient to firmly establish the simultaneously observed NO_x concentrations. In addition, low concentration ratios of [HNO₃]/[NO_x] imply that the photochemical production of NO_x within the snow pack can influence surface NO_x mixing ratios in Antarctica. Alternate measurements of PAN mixing ratios at two different heights above the snow surface were performed to derive fluxes between the lower troposphere and the underlying snow pack using calculated friction velocities. Most of the concentration differences were below the precision of the measurements. Therefore, only an upper limit for the PAN flux of ±1×10¹³ molecules m⁻² s⁻¹ without a predominant direction can be estimated. However, PAN fluxes below this limit can still influence both the transfer of nitrogen compounds between atmosphere and ice, and the PAN budget in higher southern latitudes.     

Stochastic analysis to assess the spatial distribution of groundwater nitrate concentrations in the Po catchment (Italy)

A large database including temporal trends of physical, ecological and socio-economic data was developed within the EUROCAT project. The aim was to estimate the nutrient fluxes for different socio-economic scenarios at catchment and coastal zone level of the Po catchment (Northern Italy) with reference to the Water Quality Objectives reported in the Water Framework Directive (WFD 2000/60/CE) and also in Italian legislation. Emission data derived from different sources at national, regional and local levels are referred to point and non-point sources. While non-point (diffuse) sources are simply integrated into the nutrient flux model, point sources are irregularly distributed. Intensive farming activity in the Po valley is one of the main Pressure factors Driving groundwater pollution in the catchment, therefore understanding the spatial variability of groundwater nitrate concentrations is a critical issue to be considered in developing a Water Quality Management Plan. In order to use the scattered point source data as input in our biogeochemical and transport models, it was necessary to predict their values and associated uncertainty at unsampled locations. This study reports the spatial distribution and uncertainty of groundwater nitrate concentration at a test site of the Po watershed using a probabilistic approach. Our approach was based on geostatistical sequential Gaussian simulation used to yield a series of stochastic images characterized by equally probable spatial distributions of the nitrate concentration across the area. Post-processing of many simulations allowed the mapping of contaminated and uncontaminated areas and provided a model for the uncertainty in the spatial distribution of nitrate concentrations.     

Seasonal evolutions of ozone (O3) and its nitrogen precursors (NO, NO2) in urban Sfax (Tunisia)

Seasonal evolution of ozone (O3) and its nitrogen precursors (NO, NO2) in downtown Sfax (Tunisia) was monitored. Nitrogen oxides are shown to be closely related to local vehicle sources. Seasonal ozone levels, however, are shown to be dependent on regional meteorological conditions. High ozone levels are due to the effect of anticyclones and stratosphere intrusions (cut-off lows). Low levels are associated with cyclonic conditions of small vertical range of motion. Other than these particular conditions, ozone levels are shown to be relatively higher in fall and winter seasons, characterised by a very steady atmosphere. Overall, the examined meteorological conditions, the ozone concentrations observed in downtown Sfax are characterised by clear day/night cycles, which can be explained by the significant ventilation of the region.     

Trends in nitrate concentrations and determination of its origin using stable isotopes (18O and 15N) in groundwater of the Western Central Valley, Costa Rica

A study was conducted to evaluate long-term trends in nitrate concentrations and to try to identify the origin of nitrate using stable isotopes (15N(NO3-) and 18O(NO3-)) in the aquifers of the western Central Valley, Costa Rica, where more than 1 million people depend on groundwater to satisfy their daily needs. Data from 20 sites periodically sampled for 4 to 17 years indicate an increasing trend in nitrate concentrations at five sites, which in a period ranging from 10 to 40 years, will exceed recommended maximum concentrations. Results of isotopic analysis indicate a correspondence between land use patterns and the isotopic signature of nitrate in groundwater and suggest that urbanization processes without adequate waste disposal systems, followed by coffee fertilization practices, are threatening water quality in the region. We conclude that groundwater management in this area is not sustainable, and that land use substitution processes from agricultural activity to residential occupation that do not have proper sewage disposal systems may cause a significant increment in the nitrate contaminant load.     

Validation of regression models for nitrate concentrations in the upper groundwater in sandy soils

For Dutch sandy regions, linear regression models have been developed that predict nitrate concentrations in the upper groundwater on the basis of residual nitrate contents in the soil in autumn. The objective of our study was to validate these regression models for one particular sandy region dominated by dairy farming. No data from this area were used for calibrating the regression models. The model was validated by additional probability sampling. This sample was used to estimate errors in 1) the predicted areal fractions where the EU standard of 50 mg l⁻¹ is exceeded for farms with low N surpluses (ALT) and farms with higher N surpluses (REF); 2) predicted cumulative frequency distributions of nitrate concentration for both groups of farms.Both the errors in the predicted areal fractions as well as the errors in the predicted cumulative frequency distributions indicate that the regression models are invalid for the sandy soils of this study area.     

Natural sunlight NO(3)(-)/NO(2)(-)-induced photo-degradation of phenylurea herbicides in water

The nitrate-induced photodegradation of phenylureas in water was demonstrated to occur efficiently using natural sunlight irradiation. The kinetics of disappearance was found to be dependent on the inducer and substrate concentrations, the phenylurea structure and the origin and composition of the aqueous matrix including the presence of nitrite. The measured effects under sunlight were of the same order of those measured previously in the lab using our solar light simulated system. However, by-product distribution might differ substantially particularly considering the nitration pathway.     

Methodology for the analysis of Peroxyacetyl nitrate (PAN) in the unpolluted atmosphere

A light weight electron capture, gas chromatograph has been laboratory- and field-tested to conduct surface and airborne PAN measurements in the unpolluted troposphere. A dynamic calibration system based on CH₃CHO/NO₂/Cl₂ photolysis studies by Gay et al. (1976) was constructed and successfully tested. PAN was cryogenically preconcentrated prior to analysis. A sensitivity of 5 parts per trillion (ppt) and an overall accuracy of ± 20 % is estimated. It is shown that gas phase coulometry (GPC) is unsuited for absolute PAN analysis—principally, because a significant fraction of PAN is destroyed prior to coulometric detection. The kinetics of this destruction process are nonlinear. PAN measurements at a marine Pacific site, and aboard an aircraft, show that PAN is always present at a concentration range of 10–100 ppt, although concentrations as high as 400 ppt were measured at an altitude of 4.6 km over the Pacific Ocean. Surface PAN measurements at a Pacific marine site indicate a distinct diurnal behavior, tentatively attributed to photochemistry involving alkenes, alkanes and NO_x. There was no evidence of PAN diurnal variation in the free troposphere, but the data are currently too sparse. Measurements in the global atmosphere are needed to accurately describe the distribution and the role of PAN in the chemistry of the natural atmosphere.     

Peroxyacetyl nitrate (PAN) in the urban atmosphere

Peroxyacetyl nitrate (PAN) in air has been well known as the indicator of photochemical smog due to its frequent occurrences in Seoul metropolitan area. This study was implemented to assess the distribution characteristics of atmospheric PAN in association with relevant parameters measured concurrently. During a full year period in 2011, PAN was continuously measured at hourly intervals at two monitoring sites, Gwang Jin (GJ) and Gang Seo (GS) in the megacity of Seoul, South Korea. The annual mean concentrations of PAN during the study period were 0.64 ± 0.49 and 0.57 ± 0.46 ppb, respectively. The seasonal trends of PAN generally exhibited dual peaks in both early spring and fall, regardless of sites. Their diurnal trends were fairly comparable to each other. There was a slight time lag (e.g., 1 h) in the peak occurrence pattern between O₃ and PAN, as the latter trended to peak after the maximum UV irradiance period (16:00 (GJ) and 17:00 (GS)). The concentrations of PAN generally exhibited strong correlations with particulates. The results of this study suggest that PAN concentrations were affected sensitively by atmospheric stability, the wet deposition of NO₂, wind direction, and other factors.     

Evidence for destruction of PCBs by the OH radical in urban atmospheres

Evidence for reaction of polychlorinated biphenyl (PCB) congeners with the hydroxyl (OH) radical in the troposphere was observed in diurnal variations in ambient gas-phase PCB concentrations at three urban sampling sites located in the Chicago, IL; Baltimore, MD; and Jersey City, NJ urban/industrial areas. The magnitude of the depletion of individual PCB congeners decreased by about 10-20% for each additional chlorine substituent, reflecting slower reaction rates for higher MW congeners with the OH radical. Octa- and nonachlorobiphenyls, which are largely unreactive with the OH radical, were used as tracers to investigate the effects of dilution on diurnal variation. The environmental rate constants for disappearance of the PCBs range from about 1.0 day(-1) for trichlorobiphenyls to about 0.3 day(-1) for hexachlorobiphenyls. Assuming a OH radical concentration of 3 x 10(6) molecules cm (-3), the second-order rate constants for reaction of specific congeners with the OH radical are consistent with laboratory measurements. More importantly, the relative reactivity of PCB homologues agrees well with the relationship predicted by other researchers from laboratory measurements, suggesting that losses of PCBs during daytime tropospheric transport are due at least in part to reactions with the OH radical.     

Polynuclear aromatic hydrocarbon contaminants in oysters from the Gulf of Mexico (1986-1990)

Polynuclear aromatic hydrocarbon (PAH) contaminant concentrations in 870 composite oyster samples from coastal and estuarine areas of the Gulf of Mexico analyzed as part of National Oceanographic and Atmospheric Administration's (NOAA's) National Status and Trends (NS&T) Mussel Watch Program exhibit a log-normal distribution. There are two major populations in the data. The cumulative frequency function was used to deconvolute the data distribution into two probability density functions and calculate summary statistics for each population. The first population consists of sites with lower PAH concentration probably due to background contamination (i.e. stormwater runoff, atmospheric deposition). The second population are sites with higher concentrations of PAHs associated with local point sources of PAH input (i.e. small oil spills, etc.). The temporal pattern for the mean concentration of the populations from the Gulf of Mexico is consistent with large-scale climatic factors such as the El Ni?o cycles which affect the precipitation regime.     

Compilation of a database on the composition of anthropogenic VOC emissions for atmospheric modeling in Europe

To analyse and generate air pollution control strategies and policies, e.g. efficient abatement strategies or action plans that lead to a fulfilment of air quality aims, atmospheric dispersion models (CTMs) have to be used. These models include a chemical model, where the numerous volatile organic compounds (VOCs) species are lumped together in classes. On the other hand, emission inventories usually report only total non-methane VOC (NMVOC), but not a subdivision into these classes. Thus, VOC species profiles are needed that resolve total NMVOC emission data. The objective of this publication is to present the results of a compilation of VOC species profiles that dissolve total VOC into single-species profiles for all relevant anthropogenic emission source categories and the European situation. As in atmospheric dispersion models usually modules for generating biogenic emissions are directly included, only anthropogenic emissions are addressed. VOC species profiles for 87 emission source categories have been developed. The underlying data base can be used to generate the data for all chemical mechanisms. The species profiles have been generated using recent measurements and studies on VOC species resolution and thus represent the current state of knowledge in this area. The results can be used to create input data for atmospheric dispersion models in Europe.The profiles, especially those for solvent use, still show large uncertainties. There is still an enormous need for further measurements to achieve an improved species resolution. In addition, the solvent use directive and the DECOPAINT directive of the European Commission will result in a change of the composition of paints; more water-based and high-solid paints will be used; thus the species resolution will change drastically in the next years. Of course, the species resolution for combustion and production processes also requires further improvement.     

Hydroxyl radical (OH) yields from the ozonolysis of both double bonds for five monoterpenes

A new method has been applied to determine OH-radical yields from the ozonolysis of both double bonds from five selected, atmospherically relevant monoterpenes, namely terpinolene, α-phellandrene, limonene, α-terpinene and γ-terpinene. While OH-yields for the faster reacting double bond agreed with previous literature values, the yields from the second double bond were determined for the first time and are as follows: limonene 7–10%, terpinolene 39–48%, α-phellandrene 8–11% and α-terpinene 12–14%. Only for γ-terpinene the rate coefficient for the reaction of ozone with the two double bonds was too similar in order to distinguish the OH-yield with this method. In all cases the yield from the second double bond was significantly lower than the first. The reasons for this difference are discussed in terms of the Criegee-intermediate reactions, in particular the number of abstractable H-atoms and the number of possible hydroperoxide products.     

Field observations of regional and urban impacts on NO2, ozone,UVB, and nitrate radical production rates in the Phoenix air basin

In the May and June of 1998, field measurements were taken at a site near the Usery Pass Recreation Area, ∼27 miles from the downtown Phoenix area, overlooking Phoenix and Mesa, Arizona. This site was selected to examine the impacts of the Phoenix urban plume on the Usery Pass Recreation Area and surrounding regions. Data were obtained for ultraviolet-B (UVB) radiation, nitrogen dioxide (NO₂), peroxyacetyl nitrate (PAN), ozone (O₃), and carbon monoxide (CO). Nocturnal plumes of NO₂ (in tens of ppb), observed near midnight, were correlated with CO and anti-correlated with O₃. This behavior was consistent with the titration of locally generated NO by boundary layer O₃ to form the nighttime NO₂ plumes that were subsequently transported into the Usery Pass Recreation area. Nitrate radical (NO₃) production rates were calculated to be very high on the edges of these nocturnal plumes. Examination of O₃ and PAN data also indicates that Phoenix is being affected by long-range transport of pollutants from the Los Angeles to San Diego areas. A regional smoke episode was observed in May, accompanied by a decrease in UVB of factor of two and a decrease in O₃ and an increase in methyl chloride. Low level back trajectories and chemical evidence confirm that the smoke event originated in northern Mexico and that the reduced O₃ levels observed at Usery Pass could be partially due to reduced photolysis rates caused by carbonaceous soot aerosols transported in the smoke plume. The results are discussed with regard to potential effects of local pollution transport from the Phoenix air basin as well as an assessment of the contributions from long-range transport of pollutants to the background levels in the Phoenix-Usery Pass area.     

Radical/radical vs radical/molecule reactions in the formation of PCDD/Fs from (chloro)phenols in incinerators

Pathways from chlorinated phenols as precursors to PCDD/Fs are discussed with focus on the effect of (poly)chlorination on thermochemistry and rate in the displacement of chlorine from a chlorophenol molecule by a (chloro)phenoxy radical (reaction (A) as a key example). Through measurements on the respective methylethers (anisoles) the O-H bond of 2,4,6-TCP turns out to be 5 kcal/ mol, and that in PCP 4 kcal/mol, less strong than O-H in phenol itself. On this basis it is concluded that-in contrast with earlier proposals--displacements such as in reaction (A) are at least as slow as reaction (B) of phenoxy radical with chlorobenzene. PhO. + PhCl -->PhOPh + Cl. reaction B Compared with condensation of two (chloro)phenoxy radicals, such radical/molecule reactions are therefore an insignificant pathway to dioxins in incinerators.     

PVA-Ca(NO3)2法固定化氧化亚铁硫杆菌对Fe2+的氧化及动力学研究

把聚乙烯醇(PVA)、海藻酸钠和氧化亚铁硫杆菌混合水溶胶滴入1%～5%(质量分数)的Ca(NO3)2溶液中凝固成型,并把成型后的颗粒置低温冷冻,形成固定化颗粒.用该颗粒填充固定床生物反应器进行连续操作,考察了不同稀释率下固定床生化反应器氧化Fe2 的情况,在温度30 ℃、pH1.8、稀释率0.5 h-1条件下,Fe2 最大氧化速率达2.90 g/(L·h).而且固定化操作简单,即使在没有灭菌的情况下,稳定性保持良好,具有较好的应用前景.