Pb isotopic ratios in airborne PM10 of an iron/metal industrial complex area and nearby residential areas: Implications for ambient sources of Pb pollution

This study examined four stable isotopic compositions of Pb in the PM₁₀ (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb) along with the ambient Pb concentrations in two residences relative to their proximity to an iron and metal industrial complex (IMIC) as well as an industrial site located within the boundary of the IMIC. In addition, eight potential emission sources were investigated for stable isotopic compositions of Pb. The wintertime Pb isotopic ratios for ²⁰⁸Pb/²⁰⁶Pb for ambient samples of an industrial sampling site (ISS) were closer to those of the residential ambient air concentrations measured at closer proximity to the IMIC (RA1) compared to another residential area located further away (RA2). This finding suggests that the ambient Pb sources were more similar between RA1 and the ISS than between RA2 and the ISS. In contrast, the summertime Pb isotopic ratios for the ambient samples of the ISS were not similar to those for RA1, which in turn were similar to those for RA2. During the summer, it is suggested that motor vehicle emissions appear to be a potential source of Pb in the two residential areas. For the ISS, neither ²⁰⁷Pb/²⁰⁶Pb nor ²⁰⁸Pb/²⁰⁶Pb ratios showed a clear seasonal pattern. However for the ambient samples of the two residential areas, both the ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios exhibited a seasonal pattern, with relatively higher mean ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios during the summer season. It was further confirmed that the ambient Pb concentrations were significantly higher at the ISS than those for RA1, which in turn were significantly higher than those for RA2. At all three sampling sites, high enrichment factor values (≥ 475) were found for Pb.     

环球海洋大气气溶胶化学研究 III：金属形态和入海通量

中国第三次南极考察和环球科学考察，历经北太平洋、南太平洋、南极半岛海域、南大西洋、北印度洋、以及沿途近岸海域，共收集58个气溶胶样品，采用石墨炉原子吸收法分析其中的水可溶态和酸可溶态的Mn、Fe、Pb、Cu、Cd。气溶胶中金属表现明显陆源向大洋输送的浓度梯度，近岸海域上空金属含量大于大洋上空含量，北太平洋上空含量高于南太平洋和南极半岛海域。气溶胶中金属的水可溶程度，在近岸海域上空依次为Cd＞Mn＞Cu＞Fe＞Pb，百分比分量分别为39%，36%， 23%，14%和5.3%；在大洋上空依次为Cd＞Mn＞Fe＞Cu＞pb，百分比分量分别为62%，44%，11%，3.1%和2.5%。本文还计算和比较各观测海区上空金属从大气输入海水的通量。     

Inorganic ions and trace metals bulk deposition at an Atlantic Coastal European region

The inorganic chemical composition (major ions and trace metals) of bulk deposition samples collected monthly with bulk collectors at seven Atlantic Coastal European cities (Galicia, Northwest of Spain) during wet season (September 2011 to March 2012) has been assessed and compared. Trace metals (Al, As, Ba, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn) were analysed in soluble fraction and non-soluble fraction (after acid extraction) of the bulk deposition by inductively coupled plasma-mass spectrometry. Major inorganic ions (Cl^?, NO₃ ^?, SO₄ ^2?, Na⁺, K⁺, Ca²⁺, Mg²⁺ and NH₄ ⁺) were analysed in the soluble fraction of the bulk deposition by capillary zone electrophoresis. Univariate analysis (ANOVA and Multiple Range Test) according to the location of each sampling site was performed. Results also suggest a great influence of cleaner Atlantic air masses. After partition coefficients and enrichment factor estimation, similar sources could be assigned for the ionic and metal composition of bulk deposition at seven urban sites.     

Size distributions of ambient air particles and enrichment factor analyses of metallic elements at Taichung Harbor near the Taiwan Strait

This work attempts to characterize metallic elements associated with atmospheric particulate matter on a dry deposition plate, a TE-PUF high-volume air sampler and a universal air sampler. Dry deposition fluxes of particulates and concentrations of total suspended particulate, fine (PM_2.5) and coarse (PM_2.5–10) particulate matters were collected at Taichung harbor sampling sites from August 2004 to January 2005. Chemical analyses of metallic elements were made using a flame atomic absorption spectrophotometer coupled with hollow cathode lamps. Concentrations of metal elements in the forms of coarse particles and fine particles as well as the coarse/fine particulate ratios were presented. Statistical methods such as correlation analysis, principal component analysis and enrichment factor analysis were performed to compare the chemical components and identify possible emission sources at the sampling sites. Metallic elements of Cu, Zn, Pb, Cr, Ni and Mg had higher EF_crust ratios in winter and spring than in summer and autumn. Diurnal and nocturnal variations of metallic element concentrations in fine and coarse particles were also discussed.     

Heavy metals in aerosol samples from the Eastern Pamirs collected 2004–2006

This study measured the concentration of heavy metal elements in atmospheric aerosol samples collected between July 2004 and April 2006 at a remote site on Mt. Muztagata (38°17'N, 75°01'E, 4430 m), in the Eastern Pamirs. Inductively coupled plasma mass spectroscopy (ICP–MS) results show that the air at Muztagata contains low concentrations of As and heavy metal elements (Cr, Ni, Cu, Zn, Cd, Pb, and Bi), comparable with those in the Arctic — far lower than in heavily populated or industrialized areas. Observed enrichment factor (EF) values greater than 10 for those elements suggest partly anthropogenic sources. Seasonal variations in the concentrations of Zn, Cd, Pb, Bi, and As resemble those of crustal Al, with greater concentrations during the summer but lower ones in winter. Our results reveal that the background atmosphere in remote inner Asia is only weakly affected by anthropogenic pollution, and demonstrate that high heavy metal concentrations occur during summer but with greater EF values during the winter. The air mass back-trajectory analyses suggest that pollution from West Asia, Central Asia, and South Asia are the main possible source areas that contribute to the heavy metals in aerosols at Muztagata.     

Elemental composition of PM2.5 and PM10 at Mount Gongga in China during 2006

In order to investigate the chemical characteristics of atmospheric aerosols in a regional background site, PM_2.5 and PM₁₀ were collected at Mount Gongga Station once a week in 2006. The concentrations of fifteen elements including Na, Mg, Al, K, Ca, V, Fe, Ni, Cu, Zn, As, Ag, Ba, Tl, and Pb were detected by Inductively Coupled Plasma Mass Spectrometer (ICP-MS). The results showed that Na, Mg, Al, K, Ca, Fe were the major components of elements detected in PM_2.5 and PM₁₀, occupied 89.5% and 91.3% of all the elements. Crustal enrichment factor (EF) calculation indicated that several anthropogenic heavy metals (Ni, Cu, Zn, As, Ag, Tl, Pb) were transported long distances atmospherically. The concentrations of all elements (except Na) measured in PM_2.5 and PM₁₀ in spring and winter were higher than those in summer and autumn. The backward air mass trajectory analysis suggests that northeast India may be the source region of those pollutants.     

Validation of very high cloud droplet number concentrations in air masses transported thousands of kilometres over the ocean

The microstructure of orographic clouds related to the aerosol present was studied during the second Aerosol Characterisation Experiment (ACE‐2). Very high cloud droplet number concentrations (almost 3000 cm⁻³) were observed. These high concentrations occurred when clouds formed on a hill slope at Tenerife in polluted air masses originating in Europe that had transported the order of 1000 km over the Atlantic Ocean. The validity of the measured droplet number concentrations was investigated by comparing with measurements of the aerosol upstream of the cloud and cloud interstitial aerosol. Guided by distributions of the ratios between the measurements, three criteria of typically 30% in maximum deviation were applied to the measurements to test their validity. Agreement was found for 88% of the cases. The validated data set spans droplet number concentrations of 150–3000 cm⁻³. The updraught velocity during the cloud formation was estimated to 2.2 m s⁻¹ by model calculations, which is typical of cumuliform clouds. The results of the present study are discussed in relation to cloud droplet number concentrations previously reported in the literature. The importance of promoting the mechanistic understanding of the aerosol/cloud interaction and the use of validation procedures of cloud microphysical parameters is stressed in relation to the assessment of the indirect climatic effect of aerosols.     

Trace gases and PM2.5-bound metal abundance over a tropical urban environment,South India

Pre and Post-Monsoon levels of ambient SO₂, NO₂, PM_2.5 and the trace metals Fe, Cu, etc. were measured at industrial and residential regions of the Kochi urban area in South India for a period of two years. The mean PM_2.5, SO₂ and NO₂ concentrations across all sites were 38.98?±?1.38 µg/m³, 2.78?±?0.85 µg/m³ and 11.90?±?4.68 µg/m³ respectively, which is lower than many other Indian cities. There was little difference in any on the measured species between the seasons. A few sites exceeded the NAAQS (define acronym and state standard) and most of the sites exceeded WHO (define acronym and state standard) standard for PM_2.5. The average trace metal concentrations (ng/m³) were found to be Fe (32.58)?>?Zn (31.93)?>?Ni (10.13)?>?Cr (5.48)?>?Pb (5.37)?>?Cu (3.24). The maximum concentration of trace metals except Pb were reported in industrial areas. The enrichment factor, of metals relative to crustal material, indicated anthropogenic dominance over natural sources for the trace metal concentration in Kochi’s atmosphere. This work demonstrates the importance of air quality monitoring in this area.

     

Short-Term Variability of Atmospheric DMS and Its Oxidation Products at Amsterdam Island during Summer Time

A one-month experiment was performed at Amsterdam Island in January 1998, to investigate the factors controlling the short-term variations of atmospheric dimethylsulfide (DMS) and its oxidation products in the mid-latitudes remote marine atmosphere. High mixing ratios of DMS, sulfur dioxide (SO₂) and dimethylsulfoxide (DMSO) have been observed during this experiment, with mean concentrations of 395 parts per trillion by volume (pptv) (standard deviation, = 285, n = 500), 114 pptv ( = 125, n = 12) and 3 pptv ( = 1.2, n = 167), respectively. Wind speed and direction were identified as the major factors controlling atmospheric DMS levels. Changes in air temperature/air masses origin were found to strongly influence the dimethylsulfoxide (DMSO)/DMS and SO₂/DMS molar ratios, in line with recent laboratory data. Methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^2–) mean concentrations in aerosols during this experiment were 12.2± 6.5 pptv (1, n=47) and 59 ± 33 pptv (1, n=47), respectively. Evidence of vertical entrainment was reported following frontal passages, with injection of moisture-poor, ozone-rich air. High MSA/ nss-SO₄ ^2– molar ratios (mean 0.44) were calculated during these events. Finally following frontal passages, few spots in condensation nuclei (CN) concentration were also observed.     

南京地区冬季大气冰核特征及其与气溶胶关系的研究

2011年11月15日～12月2日期间对南京地区近地面大气气溶胶和冰核进行了同步观测,综合分析了 冰核浓度的特征及其与气溶胶粒子浓度的关系。结果表明:活化温度T_a为-20℃,水面过饱和度为1%时,南京地区冰核浓度N_IN为0.352 L-1,与0.01～10 μm气溶胶数浓度比值仅为4×10-8。冰核活化温度越低,湿度越大,冰核浓度越高。雾和降雨对冰核都有明显的清除作用。对比不同气团对南京地区冰核的影响发现,偏东方向的污染气团中冰核以及气溶胶的浓度最高,但是来自西北地区的气团中冰核占气溶胶的比例最高,这可能是由于冰相核化能力较强的沙尘气溶胶导致的。分析冰核与不同粒径段气溶胶的相关性发现,较大粒径气溶胶的表面积浓度与冰核相关性更高,本文也得到了由活化温度T_a和粒径大于0.5 μm气溶胶数浓度N_{0.5～10 μm}共同计算冰核浓度的经验公式。     

Application of Lead Isotopic Ratios in Atmospheric Pollution Studies in the Valley of Mexico

Lead isotopic studies of airborne particulate matter, gasoline and other environmental samples have been carried out to determine possible sources of lead pollution in the Metropolitan Zone of the Valley of Mexico. ²⁰⁶Pb/²⁰⁷Pb ratio in gasoline was 1.1395 ± 0.0165 and 1.071 ± 0.008 for industrially-derived lead as a mean. Natural lead is more radiogenic with values from 1.2082 ± 0.022 to 1.211 ± 0.108. The measured Pb isotopic signature of airborne particulate matter reflects the relative importance of each of these sources. The ²⁰⁶Pb/²⁰⁷Pb ratio was 1.179 ± 0.105 as a mean. The relative importance of gasoline has decreased, and, therefore, other sources (natural and industrial) can be identified by means of isotopic studies. This is a consequence of the introduction of unleaded gasoline as mandaped by strictest environmental regulation.     

Chemical composition of aerosols in the atmosphere of Mongolia

Presented are the results of studies of the component composition of atmospheric aerosols in Mongolia for the period of 2005?C2010. It is demonstrated that the local emissions mostly affect the composition of aerosols in industrial cities (Ulan Bator and Sükhbaatar), whereas the distant transport of pollutants and the wind regime of the area, in particular, the dust storms affect in small towns with the undeveloped industry (Baruun-Urt and Sainshand). Revealed is the dependence of the composition and concentration of suspended particles on the meteorological conditions in the research area. High concentrations of aerosols were observed on the days with strong winds and air masses transport from the deserts and industrial areas of China. Low concentrations of ions were observed during periods of calm weather and in case of the air masses transport from the territories of Russia and Kazakhstan.     

Occurrence of water soluble organic nitrogen in aerosols at a coastal area

Aerosol samples (205) were collected from January 2005 to November 2006 at a coastal site at Keelung City (Taiwan), on the southern East China Sea. The atmospheric concentrations of major ions indicated that the area was dominated by different air masses at different times of the year: continental Asia from January to May and November to December; air masses from Indonesia and surrounding islands (south-eastern region) dominated during early-summer (July 2005 and June 2006), and air masses directly from the adjacent ocean dominated during late-summer (July to August 2006) and early-autumn (September to October 2005). The atmospheric concentrations of water soluble organic nitrogen (WSON) corresponded to the different sources and weather conditions. The results of a factor analysis of combined major ions, water soluble inorganic nitrogen (WSIN) and WSON indicated that a fossil fuel combustion source and biomass burning were the two major controlling factors during the sampling period. We discuss the correlations between WSON, WSIN and major anthropogenic ions in relation to the different formation mechanisms for the various sources. We propose a mechanism whereby biomass burning is the major input of aerosols derived from mainland China. Fossil fuel combustion was found to be important during periods when aerosols were derived from the south-eastern area. Our data indicate that WSON was predominantly associated with aerosols derived from biomass burning when the origin of the air mass was mainland China.     

Biomonitoring of heavy metals by <Emphasis Type="Italic">Pseudevernia furfuracea</Emphasis> (L.) Zopf in Ankara (Turkey)

The objective of this study was to determine the air pollution level of Ankara and to generate the air pollution map of this city by using Pseudevernia furfuracea (L.) Zopf as a biomonitor. Lichen samples were collected from unpolluted area at Yaprakli Mountains, Cankiri in November 2002 and transplanted to 27 localities in Ankara. Lichen samples were retrieved following an exposure of 3 and 6 months. Heavy metal, Cu, Mn, Ni, Pb and Zn, contents were determined by using inductively coupled plasma spectrometry (ICP). The chlorophyll a and b contents were determined by using DMSO method. The increase in Ni, Pb, Zn and chlorophyll a content of the specimens were statistically important. All the increases and decreases in the variables could be explained by the environmental stress like pollution, but it is hard to say that this is the only reason of these changes, also climatic conditions, seasons, strength of the light and the physiological status of the plant itself effective on these changes. According to the results of heavy metal analysis Pseudevernia furfuracea continued to accumulate heavy metals and worked well as a biomonitor. The air pollution level of Ankara shows great variations because of the great area of the city.     

Cloud condensation nuclei measurements at Mace Head, Ireland, over the period 1994–2002

Analyses of cloud condensation nuclei (CCN) number concentrations (cm^− 3) measured at the Mace Head Atmospheric Research Station, near Carna, County Galway, Ireland, using a DH Associates Model M1 static thermal diffusion cloud chamber over the period from March 1994 to September 2002 are presented in this work. Air masses are defined as being ‘marine’ if they originate from a wind direction of 180–300° and ‘continental’ air masses are defined as originating from a wind direction of 45–135°. Air masses without such filtering were classified as ‘undefined’ air masses. Air masses were found to be dominated by marine sector air, re-affirming Mace Head as a baseline atmospheric research station. CCN levels for specific air masses at Mace Head were found to be comparable with earlier studies both at Mace Head and elsewhere. Monthly averaged clean marine (wind direction of 180–300° and black carbon absorption coefficient < 1.425 Mm^− 1) CCN and marine CCN varied between 15–247 cm^− 3 and 54–670 cm^− 3, respectively. As expected, significant increases in number concentration were found in continentally sourced CCN over that of marine CCN and were found to follow a log-normal distribution significantly tighter than that of clean marine air masses. No significant trend was found for CCN over the 9-year period. While polluted continental air masses showed a slight increase in CCN concentrations over the winter months, most likely due to increased fuel usage and a lower mixed boundary layer, the dominance of marine sector air arriving at Mace Head, which generally consists of background CCN concentrations, reduced seasonal differences for polluted air. Marine air showed a distinct seasonal pattern, with elevated values occurring over the spring and summer seasons. This is thought to be due to enhanced biogenic aerosol production as a result of phytoplankton bloom activity in the North Atlantic.     

A DIAGNOSTIC ANALYSIS OF AIR TEMPERATURE ANOMALY MODE OVER CHINA IN 2009/2010 WINTER BASED ON GENERALIZED EQUILIBRIUM FEEDBACK ASSESSMENT (GEFA) METHOD

By using the observed monthly mean data over 160 stations of China and NCAR/NCEP reanalysis data, the generalized equilibrium feedback assessment(GEFA) method, combined with the methods of EOF analysis, correlation and composite analysis, is used to explore the influence of different SST modes on a wintertime air temperature pattern in which it is cold in the northeast and warm in the southwest in China. The results show that the 2009/2010 winter air temperature oscillation mode between the northern and southern part of China is closely related to the corresponding sea surface temperature anomalies(SSTA) and its associated atmospheric circulation anomalies. Exhibiting warming in Northeast China and cooling in Southwest China, the mode is significantly forced by the El Nio mode and the North Atlantic SSTA mode, which have three poles. Under the influence of SSTA modes, the surface northerly flow transported cold air to North and Northeast China, resulting in low temperatures in the regions. Meanwhile, the mid-latitude westerlies intensify and the polar cold air stays in high latitudes and cannot affect the Southwest China, resulting in the warming there.     

碳质气溶胶在藏东南冰芯中的记录

在青藏高原东南部帕隆藏布源头海洋性冰川区,对冰川编目的4号冰川（PLZ-4）实施冰芯钻取,获得总长度为29 m的冰芯。对冰芯中元素碳（EC）、不溶性有机碳（WIOC）和可溶性离子（Cl-,NO3-,SO42-,Na+,K+,Mg2+,Ca2+）的含量进行实验分析,结果显示：1998-2005年上述组分在该冰芯中的含量均呈现持续增长的趋势;冰芯中EC含量及EC/WIOC比值表现出非季风季节高、季风季节低的显著特征,揭示了该地区冰川中记录的碳质气溶胶浓度与南亚棕色云之间的密切联系。同时指出,在季风前的4-5月,沉降于雪冰中平均含量＞10 ng/g的EC所引起的雪冰表面反照率降低以及冰川消融等气候环境效应不容忽视。     

Sources and Transport of Urban and Biomass Burning Aerosol Black Carbon at the South–West Atlantic Coast

The total extent of the atmospheric impacts associated to the aerosol black carbon (BC) emissions from South America is not completed described. This work presents results of BC monitored during three scientific expeditions (2002, 2003 and 2004) on board of a Brazilian oceanographic vessel Ary Rongel that covered the South–West Atlantic coast between 22–62°S. This latitudinal band encloses major urban regions of South America and the outflow region of the SACZ (South Atlantic Convergent Zone), which is an important mechanism of advective transport of heat, moisture, minor gases and aerosols from the South America continental land to the Southern Atlantic Ocean. Our results showed that aerosol BC enhanced concentrations from urban/industrial origin can be transported to the South–West Atlantic Ocean due to the migration of sub-polar fronts that frequently reach tropical/subtropical regions. Despite the decrease of aerosol BC concentrations southwards (from ∼1,200 ng m⁻³ at latitude 22°S to ∼10 ng m⁻³ at latitude 62°S), several observed peak events were attributed to regional urban activities. Most of such events could be explained by the use of air mass back trajectories analysis. In addition, a global model simulation is presented (Goddard Institute for Space Studies – GISS GCM BC simulation) to explore the origins of aerosol BC in the South–West Atlantic. The model allowed isolating the biomass emissions from South America and Africa and industrial (non-biomass) pollution from other regions of the globe. This model suggests that the apportionment of about half of the aerosol BC at the South–West Atlantic may derive from South American biomass burning.     

Highlights of fifty years of atmospheric aerosol research at Mace Head

This paper summarises the development and principal results of fifty years of research on aerosols in the marine atmosphere at Mace Head Atmospheric Research Station on the west coast of Ireland. It concentrates on the sources, physico-chemical properties, number and mass concentrations, size range, volatility and chemical composition of aerosols in different air masses. It also examines optical properties of the aerosols and their long-range transport.     

Shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide in the Caribbean and Gulf of Mexico

Simultaneous shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide were made on three cruises in the Gulf of Mexico and the Caribbean. The cruise tracks include both oligotrophic and coastal waters and the air masses sampled include both remote marine air and air masses heavily influenced by terrestrial or coastal inputs. Using samples from two north-south Caribbean transects which are thought to represent remote subtropical Atlantic air, mean concentrations of DMS and H₂S were found to be 57 pptv (74 ng S m^-3, =29 pptv, n=48) and 8.5 pptv (11 ng S m^-3, =5.3 pptv, n=36), respectively. The ranges of measured concentrations for all samples were 0–800 pptv DMS and 0–260 pptv H₂S. Elevated concentrations were found in coastal regions and over some shallow waters. Statistical analysis reveals slight nighttime maxima in the concentrations of both DMS and H₂S in the remote marine atmosphere. The diurnal nature of the H₂S data is only apparent after correcting the measurements for interference due to carbonyl sulfide. Calculations using the measured ratio of H₂S to DMS in remote marine air suggest that the oxidation of H₂S contributes only about 11% to the excess (non-seasalt) sulfate in the marine boundary layer.