Analysis of the Trend and Seasonal Cycle of Carbon Monoxide Concentrations in an Urban Area (4 pp)

Background, Aim and Scope Air quality is an field of major concern in large cities. This problem has led administrations to introduce plans and regulations to reduce pollutant emissions. The analysis of variations in the concentration of pollutants is useful when evaluating the effectiveness of these plans. However, such an analysis cannot be undertaken using standard statistical techniques, due to the fact that concentrations of atmospheric pollutants often exhibit a lack of normality and are autocorrelated. On the other hand, if long-term trends of any pollutant’s emissions are to be detected, meteorological effects must be removed from the time series analysed, due to their strong masking effects. Materials and Methods The application of statistical methods to analyse temporal variations is illustrated using monthly carbon monoxide (CO) concentrations observed at an urban site. The sampling site is located at a street intersection in central Valencia (Spain) with a high traffic density. Valencia is the third largest city in Spain. It is a typical Mediterranean city in terms of its urban structure and climatology. The sampling site started operation in January 1994 and monitored CO ground level concentrations until February 2002. Its geographic coordinates are W0°22′52″ N39°28′05″ and its altitude is 11 m. Two nonparametric trend tests are applied. One of these is robust against serial correlation with regards to the false rejection rate, when observations have a strong persistence or when the sample size per month is small. A nonparametric analysis of the homogeneity of trends between seasons is also discussed. A multiple linear regression model is used with the transformed data, including the effect of meteorological variables. The method of generalized least squares is applied to estimate the model parameters to take into account the serial dependence of the residuals of this model. This study also assesses temporal changes using the Kolmogorov-Zurbenko (KZ) filter. The KZ filter has been shown to be an effective way to remove the influence of meteorological conditions on O₃ and PM to examine underlying trends. Results The nonparametric tests indicate a decreasing, significant trend in the sampled site. The application of the linear model yields a significant decrease every twelve months of 15.8% for the average monthly CO concentration. The 95% confidence interval for the trend ranges from 13.9% to 17.7%. The seasonal cycle also provides significant results. There are no differences in trends throughout the months. The percentage of CO variance explained by the linear model is 90.3%. The KZ filter separates out long, short-term and seasonal variations in the CO series. The estimated, significant, long-term trend every year results in 10.3% with this method. The 95% confidence interval ranges from 8.8% to 11.9%. This approach explains 89.9% of the CO temporal variations. Discussion The differences between the linear model and KZ filter trend estimations are due to the fact that the KZ filter performs the analysis on the smoothed data rather than the original data. In the KZ filter trend estimation, the effect of meteorological conditions has been removed. The CO short-term componentis attributable to weather and short-term fluctuations in emissions. There is a significant seasonal cycle. This component is a result of changes in the traffic, the yearly meteorological cycle and the interactions between these two factors. There are peaks during the autumn and winter months, which have more traffic density in the sampled site. There is a minimum during the month of August, reflecting the very low level of vehicle emissions which is a direct consequence of the holiday period. Conclusions The significant, decreasing trend implies to a certain extent that the urban environment in the area is improving. This trend results from changes in overall emissions, pollutant transport, climate, policy and economics. It is also due to the effect of introducing reformulated gasoline. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of CO. The KZ filter has been the most effective method to separate the CO series components and to obtain an estimate of the long-term trend due to changes in emissions, removing the effect of meteorological conditions. Recommendations and Perspectives Air quality managers and policy-makers must understand the link between climate and pollutants to select optimal pollutant reduction strategies and avoid exceeding emission directives. This paper analyses eight years of ambient CO data at a site with a high traffic density, and provides results that are useful for decision-making. The assessment of long-term changes in air pollutants to evaluate reduction strategies has to be done while taking into account meteorological variability     

Acid Deposition in the Tuscan Appennines During the Dry Period 1988-89

The typical parameters of acid precipitation are evaluated in the forest of Vallombrosa (Tuscan Appennines) during the dry period 1988-89. Individual rain events (dry and wet deposition) were sampled in a clearing of the forest and below the canopy of an evergreen tree as well as a deciduous broadleaf tree.

In atmospheric precipitation the pH values usually vary around 4.4, with neutralization in the hot season due to calcareous material from distant sources. Relatively large concentrations of Pb and Cd are found in rain, but only in a small amount in canopy leachate. Aluminium, manganese and iron are more significantly washed off than Pb and Cd.     

Role of glycine on sulfuric acid-ammonia clusters formation: Transporter or participator

Glycine(Gly) is ubiquitous in the atmosphere and plays a vital role in new particle formation(NPF).However,the potential mechanism of its on sulfuric acid(SA)-ammonia(A)clusters formation under various atmospheric conditions is still ambiguous.Herein,a(Gly)_x·(SA)_y·(A)_z(z≤x+y≤3) multicomponent system was investigated by using density functional theory(DFT) combined with Atmospheric Cluster Dynamics Code(ACDC) at different temperatures and precursor concentrations.The results show that Gly,with one carboxyl(-COOH) and one amine(-NH_2) group,can interact strongly with SA and A in two directions through hydrogen bonds or proton transfer.Within the relevant range of atmospheric concentrations,Gly can enhance the formation rate of SA-A-based clusters,especially at low temperature,low [SA],and median [A].The enhancement(R) of Gly on NPF can be up to 340 at T=218.15 K,[SA]=10~4,[A]=10~9,and [Gly]=10~7 molecules/cm~3.In addition,the main growth paths of clusters show that Gly molecules participate into cluster formation in the initial stage and eventually leave the cluster by evaporation in subsequent cluster growth at low [Gly],it acts as an important "transporter" to connect the smaller and larger cluster.With the increase of [Gly],it acts as a "participator" directly participating in NPF.     

大气沉降向华中丘陵区稻田输入硫通量的观测

选取我国华中丘陵区的湖南省长沙县一个典型水稻种植区,对2015与2016年2年雨水样中的SO₄²-S和大气SO₂的沉降量进行监测,分析雨水中SO₄^2-、NO₃^-的关系,解析大气硫沉降的主要来源.结果表明,研究区大气中SO₂-S和雨水中SO₄^2--S的年均浓度分别为8.5 μg/m³和1.1mg/L,大气硫沉降年均总量为26.8kgS/（hm²·a）,其中年均降雨混合沉降量18.2kgS/（hm²·a）,年均干沉降量为8.6kgS/（hm²·a）.研究区域硫素干、混合沉降量存在明显的季节差异,硫素混合沉降春季高于夏、秋、冬季,而硫素干沉降冬季高于春、夏、秋季.雨水中NO₃^-/SO₄^2-的质量比大多小于1,表明研究区大气硫素主要来自固定污染源（燃煤）.华中丘陵区稻田具有较高的硫沉降,但硫沉降量已较21世纪初出现了较大幅度下降,农业生产中需要根据农田硫素收支状况酌情补充硫肥来保证作物高产稳产.     

Sulphate, Nitrogen and Base Cation Budgets at 21 Forested Catchments in Canada, the United States and Europe

To assess the concern over declining base cation levels in forest soils caused by acid deposition, input-output budgets (1990s average) for sulphate (SO₄), inorganic nitrogen (NO₃-N; NH₄-N), calcium (Ca), magnesium (Mg) and potassium (K) were synthesised for 21 forested catchments from 17 regions in Canada, the United States and Europe. Trend analysis was conducted on monthly ion concentrations in deposition and runoff when more than 9 years of data were available (14 regions, 17 sites). Annual average SO₄ deposition during the 1990s ranged between 7.3 and 28.4 kg ha⁻¹ per year, and inorganic nitrogen (N) deposition was between 2.8 and 13.8 kg ha⁻¹ per year, of which 41–67% was nitrate (NO₃-N). Over the period of record, SO₄ concentration in deposition decreased in 13/14 (13 out of 14 total) regions and SO₄ in runoff decreased at 14/17 catchments. In contrast, NO₃-N concentrations in deposition decreased in only 1/14 regions, while NH₄-N concentration patterns varied; increasing at 3/14 regions and decreasing at 2/14 regions. Nitrate concentrations in runoff decreased at 4/17 catchments and increased at only 1 site, whereas runoff levels of NH₄-N increased at 5/17 catchments. Decreasing trends in deposition were also recorded for Ca, Mg, and K at many of the catchments and on an equivalent basis, accounted for up to 131% (median 22%) of the decrease in acid anion deposition. Base cation concentrations in streams generally declined over time, with significant decreases in Ca, Mg and K occurring at 8, 9 and 7 of 17 sites respectively, which accounted for up to 133% (median 48%) of the decrease in acid anion concentration. Sulphate export exceeded input at 18/21 catchments, likely due to dry deposition and/or internal sources. The majority of N in deposition (31–100%; median 94%) was retained in the catchments, although there was a tendency for greater NO₃-N leaching at sites receiving higher (<7 kg ha^-1 per year) bulk inorganic N deposition. Mass balance calculations show that export of Ca and Mg in runoff exceeds input at all 21 catchments, but K export only exceeds input at 16/21 sites. Estimates of base cation weathering were available for 18 sites. When included in the mass balance calculation, Ca, Mg and K exports exceeded inputs at 14, 10 and 2 sites respectively. Annual Ca and Mg losses represent appreciable proportions of the current exchangeable soil Ca and Mg pools, although losses at some of the sites likely occur from weathering reactions beneath the rooting zone and there is considerable uncertainty associated with mineral weathering estimates. Critical loads for sulphur (S) and N, using a critical base cation to aluminium ratio of 10 in soil solution, are currently exceeded at 7 of the 18 sites with base cation weathering estimates. Despite reductions in SO₄ and H⁺ deposition, mass balance estimates indicate that acid deposition continues to acidify soils in many regions with losses of Ca and Mg of primary concern. The U.S. Government's right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged. The Canadian Crown reserves the right to retain a non-exclusive, royalty free licence in and to any copyright.     

Large-scale mercury variations in Lake Vänern (Sweden) 1974-98

Lake V?nern, the largest lake in Sweden, has been seriously contaminated with mercury during the 20th century. In the 1970's and 80's the direct load, mainly from a chlor-alkali industry in the area, of mercury was drastically reduced as a response to new legislation, from three to five tons down to between five and ten kg yr(-1). Large amounts of the disposed pollutant have accumulated in the sediments. The question posed in this work is now, is the effect of the drastic load reduction after more than two decades visible in the sediments? The question is relevant as large areas still are blacklisted for fishing, but also as a follow-up of a major remedy action. The lake also serves as a freshwater reservoir for even Sweden's second largest city. This work synthesises and compares data of mercury in the sediments from three major field programs, in 1974, 1984 and 1998. The interest is focused on both spatial heterogeneity and temporal trends. In 1974, the surface concentrations are significantly higher than in subsequent surveys. Significant differences are also found between 1984 and 1998. Significant spatial differences within the lake are found for respective year. The most contaminated area is located in the north, close to the major point source (a former chlor-alkali industry). This is also the area with the largest improvement, as a direct response to the reduction in load. Further from the outlet, the recovery is more affected by burial and transport processes out into the deeper basins.     

The Monitoring and Risk Assessment of Zn Deposition Around a Metal Smelter in Latvia

Heavy metal concentrations in Hylocomium splendens collected around a metal smelter in Latvia showed very high concentrations of Zn (>200 g/g), and elevated concentrations of Pb (38.3 g/g) and Cu (18.3 g/g). In an attempt to better evaluate the potential toxicity of the high Zn concentrations, a serial elution method was used to determine the concentrations of zinc in intercellular, extracellular exchangeable cell wall, intracellular, and particle fractions. The intercellular Zn concentrations represent the water soluble component of the total concentrations, and were low with no clear trends. Zn concentrations in the extra- and intracellular and particle fractions decreased exponentially from the pollutant source. Intracellular Zn concentrations in moss close to the emission source are within the range considered to be potentially toxic, from other single element exposure studies. The proportion of Zn in the relatively insoluble particle fraction, which is least associated with environmental risk, was greater closer to the pollution source, reaching > 30% in the oldest Hylocomium splendens segments.     

A Global Overview of Atmospheric Acid Deposition Fluxes

This paper presents a summary of globalacid deposition flux data taken from a globalassessment report on acid deposition prepared forUNEP/WMO (Whelpdale and Kaiser, 1996). There is a largevariation in the spacial coverage and reliability ofmonitoring around the world. Many more stationsmeasure wet deposition than collect appropriate datafor estimating dry deposition. The widespread regionswith highest precipitation concentrations anddeposition fluxes of sulphate and nitrate coincideclosely with the regions of highest density ofSO₂ and NO_x precursor emissions occurringprimarily in the mid-latitude, northern hemispherebelt where a large fraction of the worlds fossilfuels is consumed. Organic acids in precipitation makea minor contribution to acidity (<20%) inindustrial regions, but in the rest of the world theyare of same order, or even exceed, inorganic acids.Less is known about dry deposition, but it appears topredominate near strong emission sources with wetdeposition predominating farther downwind. The molarratio of the N/S contribution to acidic deposition isclose to 1.0 over large areas of Europe and NorthAmerica, but is highly variable elsewhere, beinghighest in equatorial regions due to biomass burningand lowest near smelters and other large sources of SO₂.     

大气污染物影响因素的灰色关联分析

运用灰色系统理论，对产生和影响城市大气主要污染物的相关因素，利用灰色关联分析方法进行了量化分析研究，根据研究结果，提出了控制大气污染的防治对策．     

主成份分析法在大气环境质量综合评价中的应用

介绍了主成份分析法评价大气环境质量的基本原理，并对某市的大气环境质量进行了综合评价。最后，与其它方法的评价结果进行了对比分析，进一步证实了主成份分析法的科学性、合理性。