Carbonaceous materials in size-segregated atmospheric aerosols from urban and coastal-rural areas at the Western European Coast

A high-volume cascade impactor, equipped with a PM10 inlet, was used to collect size-segregated aerosol samples during the summer of 2004 at two Portuguese locations: a coastal-rural area (Moitinhos) and an urban area (Oporto). Concentrations of airborne particulate matter (PM), total carbon (TC), organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were determined for the following particle size ranges: < 0.49, 0.49–0.95, 0.95–3.0, and 3.0–10 µm. The total PM mass concentrations at the urban and coastal-rural sites ranged from 22.8 to 79.6 μg m^− 3 and 19.9 to 28.2 μg m^− 3, respectively, and more than 56% of the total aerosol mass was found in the fractions below 3.0 μm. At both locations the highest concentrations of OC and EC were found in the submicrometer size range. The regional variability for the OC and EC concentrations, with the highest concentrations being found in the urban area, was related to the contribution of local primary sources (mostly traffic emissions). It was also verified an enrichment of the small size particles in WSOC, representing on average 37.3(± 12.4)% and 59.7(± 18.0)% of OC in the very fine aerosol at the coastal-rural and urban areas, respectively. The amount of secondary OC calculated by the minimum OC/EC ratio method indicates that secondary organic aerosol formation was important throughout the study at both sites. The obtained results suggest that long-range transport and favourable summer conditions for photochemical oxidation are key factors determining secondary OC formation in the coastal-rural and urban areas. The ultraviolet absorption properties of the chromophoric constituents of the WSOC fractions were also different among the different particle size ranges and also between the two sampling locations, thus suggesting the strong impact of the diverse emission sources into the composition of the size-segregated organic aerosol.     

Size-resolved aerosol chemical concentrations at rural and urban sites in Central California,USA

Aerosol size distributions were measured with Micro Orifice Uniform Deposit Impactor (MOUDI) cascade impactors at the rural Angiola and urban Fresno Supersites in California's San Joaquin Valley during the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) winter campaign from December 15, 2000 to February 3, 2001. PM_2.5 filter samples were collected concurrently at both sites with Sequential Filter Samplers (SFS). MOUDI nitrate (NO₃⁻) concentrations reached 66 μg/m³ on January 6, 2001 during the 1000–1600 PST (GMT-8) period. Pair-wise comparisons between PM_2.5 MOUDI and SFS concentrations revealed high correlations at the Angiola site (r > 0.93) but more variability (r < 0.85) at the Fresno site for NO₃⁻, sulfate (SO₄⁼), and ammonium (NH₄⁺). Correlations were higher at Fresno (r > 0.87) than at Angiola (r < 0.7) for organic carbon (OC), elemental carbon (EC), and total carbon (TC). NO₃⁻ and SO₄⁼ size distributions in Fresno were multi-modal and wider than the uni-modal distributions observed at Angiola. Geometric mean diameters (GMD) were smaller for OC and EC than for NO₃⁻ and SO₄⁼ at both sites. OC and EC were more concentrated on the lowest MOUDI stage (0.056 µm) at Angiola than at Fresno. The NO₃⁻ GMD increased from 0.97 to 1.02 µm as the NO₃⁻ concentration at Angiola increased from 43 to 66 µg m^− 3 during a PM_2.5 episode from January 4–7, 2001. There was a direct relationship between GMD and NO₃⁻ and SO₄⁼ concentrations at Angiola but no such relationships for OC or EC. This demonstrates that secondary aerosol formation increases both concentration and particle size for the rural California environment.     

Intraurban variability of PM10 and PM2.5 in an Eastern Mediterranean city

The results of the first large scale chemical characterization of PM10 and PM2.5 at three different sites in the urban city of Beirut, Lebanon, are presented. Between May 2009 and April 2010 a total of 304 PM10 and PM2.5 samples were collected by sampling every sixth day at three different sites in Beirut. Observed mass concentrations varied between 19.7 and 521.2 μg m^? 3 for PM10 and between 8.4 and 72.2 μg m^? 3 for PM2.5, respectively. Inorganic concentrations accounted for 29.7–35.6 μg m^? 3 and 46.0–53.5 μg m^? 3 of the total mass of PM10 and PM2.5, respectively. Intra-city temporal and spatial variations were assessed based on the study of three factors: correlation coefficients (R) for PM and chemical components, coefficient of divergence (CODs), and source apportionment using positive matrix factorization (PMF). Based on R and COD of PM concentrations, the three sites appear homogeneous. However, when individual elements were compared, heterogeneity among sites was found. This latter was attributed to the variability in the percent contribution of biogenic and local anthropogenic source factors such as traffic related sources and dust resuspension. Other factors included the proximity to the Mediterranean sea, the population density and the topographical structure of the city. Hence, despite its small size (20.8 km²), one PM monitoring site does not reflect an accurate PM level in Beirut.     

An operational MODIS aerosol retrieval algorithm at high spatial resolution,and its application over a complex urban region

Aerosol retrieval algorithms for the MODerate Resolution Imaging Spectroradiometer (MODIS) have been developed to estimate aerosol and microphysical properties of the atmosphere, which help to address aerosol climatic issues at global scale. However, higher spatial resolution aerosol products for urban areas have not been well-researched mainly due to the difficulty of differentiating aerosols from bright surfaces in urban areas. Here, an aerosol retrieval algorithm using the MODIS 500-m resolution bands is described, to retrieve aerosol properties over Hong Kong and the Pearl River Delta region. The rationale of our technique is to first estimate the aerosol reflectances by decomposing the top-of-atmosphere reflectances from surface reflectances and Rayleigh path reflectances. For the determination of surface reflectances, a Minimum Reflectance Technique (MRT) is used, and MRT images are computed for different seasons. For conversion of aerosol reflectance to aerosol optical thickness (AOT), comprehensive Look Up Tables specific to the local region are constructed, which consider aerosol properties and sun-viewing geometry in the radiative transfer calculations. Four local aerosol types, namely coastal urban, polluted urban, dust, and heavy pollution, were derived using cluster analysis on 3 years of AERONET measurements in Hong Kong. The resulting 500 m AOT images were found to be highly correlated with ground measurements from the AERONET (r² = 0.767) and Microtops II sunphotometers (r² = 0.760) in Hong Kong. This study further demonstrates the application of the fine resolution AOT images for monitoring inter-urban and intra-urban aerosol distributions and the influence of trans-boundary flows. These applications include characterization of spatial patterns of AOT within the city, and detection of regional biomass burning sources.     

Below-cloud rain scavenging of atmospheric aerosols for aerosol deposition models

Below-cloud aerosol scavenging is generally estimated from field measurements using advanced instruments that measure changes in aerosol distributions with respect to rainfall. In this study, we discuss various scavenging mechanisms and scavenging coefficients from past laboratory and field measurements. Scavenging coefficients derived from field measurements (representing natural aerosols scavenging) are two orders higher than that of theoretical ones for smaller particles (D_p < 2 μm). Measured size-resolved scavenging coefficients can be served as a better option to the default scavenging coefficient (e.g. a constant of 10^?4 s^?1 for all size of aerosols, as used in the CALPUFF model) for representing below-cloud aerosol scavenging. We propose scavenging correction parameter (C_R) as an exponential function of size-resolved scavenging coefficients, winds and width in the downwind of the source–receptor system. For a wind speed of 3 m s^?1, C_R decrease with the width in the downwind for particles of diameters D_p < 0.1 μm but C_R does not vary much for particles in the accumulation mode (0.1 < D_p < 2 μm). For a typical urban aerosol distribution, assuming 3 m s^?1 air-flow in the source–receptor system, 10 km downwind width, 2.84 mm h^?1 of rainfall and using aerosol size dependent scavenging coefficients in the C_R, scavenging of aerosols is found to be 16% in number and 24% in volume of total aerosols. Using the default scavenging coefficient (10^?4 s^?1) in the CALPUFF model, it is found to be 64% in both number and volume of total aerosols.     

Distribution of inorganic nitrogen-containing species in atmospheric particles from an island in the Yellow Sea

In this study, total suspended particles (TSP) and size-segregated atmospheric aerosol samples were measured on Qianliyan Island in the Yellow Sea in spring (April–May), summer (July–August) and fall (October–November) of 2006 and in water (January–February) of 2007. The mass concentration of the TSP varied from 75.6 to 132.0 μg/m³. The average concentration were 9.37 ± 7.56 μg/m³ and 5.32 ± 4.25 μg/m³ for nitrate and ammonium in the TSP, respectively. TSP concentration showed a significant correlation with those of nitrate (n = 27, r = 0.73) and ammonium (n = 27, r = 0.60). The mass-size distribution of atmospheric particles exhibited two modes with an accumulation mode at 0.43–1.1 μm and a coarse mode at 3.3–4.7 μm throughout the sampling months. A bi-modal size distribution of nitrate in concentration occurred in the April–May, October–November and January–February, but a uni-modal size distribution occurred in the August. The uni-modal size distribution of ammonium at 0.43–0.65 μm was observed throughout the sampling months. The average of inorganic nitrogen in mass concentration accounted for 4.0% of the total mass of aerosol particles while ammonium-N was the dominant fraction of TIN (Total Inorganic Nitrogen), contributing to 62–71% of the TIN.     

Using Föhn conditions to characterize urban and regional sources of particles

Characterizations of urban and regional sources of particulate matter (PM) were performed in the Milan area (North of Italy) during Föhn and stagnant (non-Föhn) conditions. The measurements were performed at two different places: in an urban area North of Milan (Bresso) and in a regional area at the EMEP-GAW station in Ispra (about 65 km NW from Milan) during the winter periods of the years 2002–2007. Particle size distributions and chemical bulk analysis of aerosols are combined with single particle mass spectrometry to obtain information about the chemical content of the particles and their mixing state. Föhn conditions are characterized by extremely clean background air from which background aerosol is scavenged, and consequently local sources (here defined as sources between the sampling sites and the mountain range top about 100–150 km away depending on the wind direction) determine the aerosol properties.It was observed that during Föhn events the accumulation mode in the size range 50 nm < d < 300 nm practically disappears and that the size fraction below 50 nm dominates the total number distribution. The significant change in the number size distribution and the large decrease in PM10 mass during Föhn events are accompanied by a significant change in the chemical composition of the particles. Results from bulk chemical analysis showed high amounts of carbonaceous compounds and very low concentrations of ammonium nitrate (as indicator for secondary chemistry) during Föhn episodes, in contrast to stagnant conditions, when secondary components are dominating the aerosol composition. Single particle measurements confirm the high contribution of carbonaceous compounds in locally emitted particles.It was concluded that particles that originated in the urban area come mainly from combustion processes, especially direct traffic emissions, domestic heating and industrial activities, whereas the regionally emitted particles are different with much less traffic contribution.We estimate that under prevailing (non-Föhn) winter conditions, about 50–65% of the aerosol mass load in the city of Milan are caused by local emissions, and about 35–50% come from regional background. This finding suggests that in order to improve air quality in a big city like Milan, it is important to combine local traffic restriction interventions with other long-term regional scale air-quality-measures.     

Characterization of water-soluble inorganic ions in size-segregated aerosols in coastal city,Xiamen

The samples of water-soluble inorganic ions (WSIs), including anions (F^?, Cl^?, SO₄^2?, NO₃^?) and cations (NH₄⁺, K⁺, Na⁺, Ca²⁺, Mg²⁺) in 8 size-segregated particle matter (PM), were collected using a sampler (with 8 nominal cut-sizes ranged from 0.43 to 9.0 μm) from October 2008 to September 2009 at five sites in both polluted and background regions of a coastal city, Xiamen. The results showed that particulate matters in the fine mode (PM_2.1, Dp < 2.1 μm) comprised large part of mass concentrations of aerosols, which accounted for 45.56–51.27%, 40.04–60.81%, 42.02–60.81%, and 40.46–57.07% of the total particulate mass in spring, summer, autumn, and winter, respectively. The water-soluble ionic species in the fine mode at five sampling sites varied from 15.33 to 33.82 (spring), 14.03 to 28.06 (summer), 33.47 to 72.52 (autumn), and 48.39 to 69.75 μg m^? 3 (winter), respectively, which accounted for 57.30 ± 6.51% of the PM_2.1 mass concentrations. Secondary pollutants of NH₄⁺, SO₄^2? and NO₃^? were the dominant contributors of WSIs, which suggested that pollutants from anthropogenic activities, such as SO₂, NOx were formed in aerosols by photochemical reactions. The size distributions of Na⁺, Cl^?, SO₄^2? and NO₃^? were bimodal, peaking at 0.43–0.65 μm and 3.3–5.8 μm. Although some ions, such as NH₄⁺ presented bimodal distributions, the coarse mode was insignificant compared to the fine mode. Ca²⁺ and Mg²⁺ exhibited unimodal distributions at all sampling sites, peaking at 2.1–3.3 μm, while K⁺ having a bimodal distributions with a major peak at 0.43–0.65 μm and a minor one at 3.3–4.7 μm, were used in most of samples. Seasonal and spatial variations in the size-distribution profiles suggested that meteorological conditions (seasonal patterns) and sampling locations (geographical patterns) were the main factors determining the formation of secondary aerosols and characteristics of size distributions for WSIs.     

泰山PM10及其中化学成分变化特征

为研究华北平原区域背景气溶胶成分及其变化特征,2010年6月至2011年7月在泰山顶采集了64个PM10滤膜样品,分析了样品的PM10及其中无机盐离子和有机碳（OC）、元素碳（EC）的质量浓度,并对各成分相关性等进行了分析。泰山PM10年均质量浓度约为68.4 mg/m³,其中无机盐离子约占总质量的64.8%,碳气溶胶约占17.4%。无机盐离子的质量浓度从春季逐渐增大,夏季达到峰值,秋季下降,冬季最小;OC质量浓度从春季至秋季逐渐增高,冬季最低,EC变化类似,但夏秋两季差别不大。二次有机碳（SOC）与OC的比值四季均在50%以上,年均值约为58.5%。通过后向轨迹聚类分析发现,在经过城市的较短轨迹以及南方较短混合轨迹的影响下,泰山PM10质量浓度较高,而西北长距离传输气团PM10浓度均较低。     

Characteristics of organic and elemental carbon in PM2.5 samples in Shanghai, China

Shanghai is the largest industrial and commercial city in China, and its air quality has been deteriorating for several decades. However, there are scarce researches on the level and seasonal variation of fine particle (PM_2.5) as well as the carbonaceous fractions when compared with other cities in China and around the world. In the present paper, abundance and seasonal characteristics of PM_2.5, organic carbon (OC) and elemental carbon (EC) were studied at urban and suburban sites in Shanghai during four season-representative months in 2005–2006 year. PM_2.5 samples were collected with high-vol samplers and analyzed for OC and EC using thermal-optical transmittance (TOT) protocol. Results showed that the annual average PM_2.5 concentrations were 90.3–95.5 μg/m³ at both sites, while OC and EC were 14.7–17.4 μg/m³ and 2.8–3.0 μg/m³, respectively, with the OC/EC ratios of 5.0–5.6. The carbonaceous levels ranked by the order of Beijing > Guangzhou > Shanghai > Hong Kong. The carbonaceous aerosol accounted for  30% of the PM_2.5 mass. On seasonal average, the highest OC and EC levels occurred during fall, and they were higher than the values in summer by a factor of 2. Strong correlations (r = 0.79–0.93) between OC and EC were found in the four seasons. Average level of secondary organic carbon (SOC) was 5.7–7.2 μg/m³, accounting for  30% of the total OC. Strong seasonal variation was observed for SOC with the highest value during fall, which was about two times the annual average.     

Seasonal characteristics and sources of carbonaceous components and elements of PM10 (2010–2019) in Delhi,India

In this study we present the seasonal chemical characteristics and potential sources of PM₁₀ at an urban location of Delhi, India during 2010?2019. The concentrations of carbonaceous aerosols [organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC) and water insoluble organic carbon (WIOC)] and elements (Al, Fe, Ti, Cu, Zn, Mn, Pb, Cr, F, Cl, Br, P, S, K, As, Na, Mg, Ca, B, Ni, Mo, V, Sr, Zr and Rb) in PM₁₀ were estimated to explore their possible sources. The annual average concentration (2010–2019) of PM₁₀ was computed as 227?±?97 µg m^?3 with a range of 34?734 µg m^?3. The total carbonaceous aerosols in PM₁₀ was accounted for 22.5% of PM₁₀ mass concentration, whereas elements contribution to PM₁₀ was estimated to be 17% of PM₁₀. The statistical analysis of OC vs. EC and OC vs. WSOC of PM₁₀ reveals their common sources (biomass burning and/or fossil fuel combustion) during all the seasons. Enrichment factors (EFs) of the elements and the relationship of Al with other crustal metals (Fe, Ca, Mg and Ti) of PM₁₀ indicates the abundance of mineral dust over Delhi. Principal component analysis (PCA) extracted the five major sources [industrial emission (IE), biomass burning?+?fossil fuel combustion (BB?+?FFC), soil dust, vehicular emissions (VE) and sodium and magnesium salts (SMS)] of PM₁₀ in Delhi, India. Back trajectory and cluster analysis of airmass parcel indicate that the pollutants approaching to Delhi are mainly from Pakistan, IGP region, Arabian Sea and Bay of Bengal.

     

One year measurements of aerosol optical properties over an urban coastal site: Effect on local direct radiative forcing

We present results of direct aerosol radiative forcing over a French Mediterranean coastal zone based on one year of continuous observations of aerosol optical properties during 2005–2006. Monthly-mean aerosol optical depth at 440 nm ranged between 0.1 and 0.34, with high Angstrom coefficient (α > 1.2). The single scattering albedo (at 525 nm) estimated at the surface ranged between 0.7 and 0.8, indicating significant absorption. The presence of aerosols over the Mediterranean zone during summer decreases the shortwave radiation reaching the surface by as much as 26 ± 3.9 W m^− 2, and increases the top of the atmosphere reflected radiation by as much as 5.2 ± 1.0 W m^− 2. The shortwave atmospheric absorption translates to an atmospheric heating of 2.5 to 4.6 K day^− 1. Concerted efforts are needed for investigating the possible impact of the increase in heating rate on the maintenance of heat-waves frequently occurring over this coastal region during summer time.     

Concentrations and sources of PAHs at three stations in Istanbul,Turkey

The chemical mass balance model was applied to atmospheric Polycyclic Aromatic Hydrocarbons (PAHs) in Istanbul, Turkey. A total of 326 airborne samples were collected and analyzed for 16 PAHs and Total Suspended Particles (TSP) in the September 2006–December 2007 period at three monitoring stations: Yildiz, DMO (urban sites) and Kilyos (rural site). The total average PAH concentrations were 100.66 ± 61.26, 84.63 ± 46.66 and 25.12 ± 13.34 ng m^?3 and the TSP concentrations were 101.16 ± 53.22, 152.31 ± 99.12, 49.84 ± 18.58 μg m^?3 for Yildiz, DMO and Kilyos stations respectively. At all the sites, the lighter compounds were the most abundant, notably Nap, AcPy and PA. The average correlation values between TSP and total heavier PAH were greater than 0.5 for Yildiz and DMO stations. The patterns of PAH and TSP concentrations showed spatial and temporal variations. PAH concentrations were evaluated for the PAH contribution from four sources (diesel engines, gasoline engines, natural gas combustion, and coal + wood burning). Vehicle emissions appear to be the major source with contributions of 61.2%, 63.3% and 54.1% for Yildiz, DMO and Kilyos stations respectively. Seasonal and yearly variations had different trends for all sites.     

Roadside, Urban, and Rural comparison of size distribution characteristics of PAHs and carbonaceous components of Beijing, China

Size-segregated aerosol samples were collected with a low-pressure impactor (LPI) at urban, roadside and rural sites in winter in Beijing. The size distribution of Polycyclic Aromatic Hydrocarbons (PAHs), organic carbon (OC) and elemental carbon (EC) were measured and this study focused on their size distributions and relationships of PAH to OC/EC. All PAHs show uni-modal at the accumulation mode (0.1–1.8 μm) and almost all PAHs are associated with fine particles. The absence of PAHs in the nucleus mode contributes to the coagulation under the condition of high concentration of the accumulation mode particles. The absence of PAHs in the coarse mode was probably attributed to the low temperature that restrained the redistribution of PAHs from the accumulation mode to the coarse mode. Flu(fluoranthene) and Pyr(pyrene, 4-ring) were the most abundant particulate PAHs ; however, IcdP(indeno[1,2,3-cd]pyrene) and BghiP(benzo[ghi]perylene, 6-ring) were rather low. Diagnostic ratios show vehicle and coal burning were the major sources of PAHs in winter. Ratios at rural site are obviously different from those found at roadside and urban sites. Lower value of OC/EC in the rural area than that in the urban area was probably resulted from coal burning prevailed in the rural area. OC1 and OC2 exhibit uni-mode distribution similar to their particle surface area distribution indicating their existence on particles by adsorption. OC3 and OC4 show bi-mode distribution. Grinding of biomass debris can be a probable source of OC3 and OC4 in the coarse mode. EC1 is mostly from the pyrolysis of OC; however, both the natural and anthropogenic emissions contribute to EC2. The correlation between size-segregated PAHs and carbonaceous component is also discussed to identify their sources.     

Chemical Characteristics of Carbonaceous Aerosols During Dust Storms over Xi'an in China

Characterization of carbonaceous aerosols including CC （carbonate carbon）, OC （organic carbon）, and EC （elemental carbon） were investigated at Xi＇an, China, near Asian dust source regions in spring 2002. OC varied between 8.2 and 63.7μgm^- 3, while EC ranged between 2.4 and 17.2 μ m^-3 during the observation period. OC variations followed a similar pattern to EC and the correlation coefficient between OC and EC is 0.89 （n=31）. The average percentage of total carbon （TC, sum of CC, OC, and EC） in PM2.5 during dust storm （DS） events was 13.6%, which is lower than that during non-dust storm （NDS） periods （22.7%）. CC, OC, and EC accounted for 12.9%, 70.7%, and 16.4% of TC during DS events, respectively. The average ratio of OC/EC was 5.0 in DS events and 3.3 in NDS periods. The OC-EC correlation （R^2=0.76, n=6） was good in DS events, while it was stronger （R^2=0.90, n=25） in NDS periods. The percentage of watersoluble OC （WSOC） in TC accounted for 15.7%, and varied between 13.3% and 22.3% during DS events. The distribution of eight carbon fractions indicated that local emissions such as motor vehicle exhaust were the dominant contributors to carbonaceous particles. During DS events, soil dust dominated the chemical composition, contributing 69% to the PM2.5 mass, followed by organic matter （12.8%）, sulfate （4%）, EC （2.2%）, and chloride （1.6%）. Consequently, CC was mainly entrained by Asian dust. However, even in the atmosphere near Asian dust source regions, OC and EC in atmospheric dust were controlled by local emission rather titan the transport of Asian dust.     

Evidence of high PM2.5 strong acidity in ammonia-rich atmosphere of Guangzhou,China: Transition in pathways of ambient ammonia to form aerosol ammonium at [NH4+]/[SO42–] = 1.5

In this study, 24-h PM_2.5 samples were collected using Harvard Honeycomb denuder/filter-pack system during different seasons in 2006 and 2007 at an urban site in Guangzhou, China. The particles collected in this study were generally acidic (average strong acidity ([H⁺]) ~ 70 nmol m^? 3). Interestingly, aerosol sulfate was not fully neutralized in the ammonia-rich atmosphere (NH₃ ~ 30 ppb) and even when NH₄⁺]/[SO₄^2?] was larger than 2. Consequently, strong acidity ([H⁺]) as high as 170 nmol m^? 3 was observed in these samples. The kinetic rate of neutralization of acidity (acidic sulfate) by ambient ammonia was significantly higher than the rate of formation of ammonium nitrate involving HNO₃ and NH₃ for [NH₄⁺]/[SO₄^2?] ≤ 1.5 and much lower for NH₄⁺]/[SO₄^2?] > 1.5. Therefore, higher nitrate principally formed via homogeneous gas phase reactions involving ammonia and nitric acid were observed for [NH₄⁺]/[SO₄^2?] > 1.5. However, little nitrate, probably formed via heterogeneous processes e.g. reaction of HNO₃ with sea salt or crustal species, was observed for [NH₄⁺]/[SO₄^2?] ≤ 1.5. These demonstrate a clear transition in the pathways of ambient ammonia to form aerosol ammonium at [NH₄⁺]/[SO₄^2?] = 1.5 and evidently explain the observed high acidity due to the unneutralized sulfate in the ammonium-rich aerosol (NH₄⁺]/[SO₄^2?] > 1.5). In fact, the measured acidity was almost similar to the excess acid defined as the acid that remains at [NH₄⁺]/[SO₄^2?] = 1.5 due to the un-neutralized fraction of sulfate ([H⁺] = 0.5[SO₄^2?]). The presence of high excess acid and ammonium nitrate significantly lowered the deliquescence relative humidity of ammonium sulfate (from 80% to 40%) in the ammonium-rich samples.     

Nitrate in groundwater of China: Sources and driving forces

Identifying the sources of reactive nitrogen (N) and quantifying their contributions to groundwater nitrate concentrations are critical to understanding the dynamics of groundwater nitrate contamination. Here we assessed groundwater nitrate contamination in China using literature analysis and N balance calculation in coupled human and natural systems. The source appointment via N balance was well validated by field data via literature analysis. Nitrate was detected in 96% of groundwater samples based on a common detection threshold of 0.2 mg N L^?1, and 28% of groundwater samples exceeded WHO's maximum contaminant level (10 mg N L^?1). Groundwater nitrate concentrations were the highest beneath industrial land (median: 34.6 mg N L^?1), followed by urban land (10.2 mg N L^?1), cropland (4.8 mg N L^?1), and rural human settlement (4.0 mg N L^?1), with the lowest found beneath natural land (0.8 mg N L^?1). During the period 1980–2008, total reactive N leakage to groundwater increased about 1.5 times, from 2.0 to 5.0 Tg N year^?1, in China. Despite that the contribution of cropland to the total amount of reactive N leakage to groundwater was reduced from 50 to 40% during the past three decades, cropland still was the single largest source, while the contribution from landfill rapidly increased from 10 to 34%. High reactive N leakage mainly occurred in relatively developed agricultural or urbanized regions with a large population. The amount of reactive N leakage to groundwater was mainly driven by anthropogenic factors (population, gross domestic product, urbanization rate and land use type). We constructed a high resolution map of reactive N source appointment and this could be the basis for future modeling of groundwater nitrate dynamics and for policy development on mitigation of groundwater contamination.     

Water on an urban planet: Urbanization and the reach of urban water infrastructure

Urban growth is increasing the demand for freshwater resources, yet surprisingly the water sources of the world's large cities have never been globally assessed, hampering efforts to assess the distribution and causes of urban water stress. We conducted the first global survey of the large cities’ water sources, and show that previous global hydrologic models that ignored urban water infrastructure significantly overestimated urban water stress. Large cities obtain 78 ± 3% of their water from surface sources, some of which are far away: cumulatively, large cities moved 504 billion liters a day (184 km³ yr⁻¹) a distance of 27,000 ± 3800 km, and the upstream contributing area of urban water sources is 41% of the global land surface. Despite this infrastructure, one in four cities, containing $4.8 ± 0.7 trillion in economic activity, remain water stressed due to geographical and financial limitations. The strategic management of these cities’ water sources is therefore important for the future of the global economy.     

Past and future carbon sequestration benefits of China’s grain for green program

Carbon sequestration through ecological restoration programs is an increasingly important option to reduce the rise of atmospheric carbon dioxide concentration. China’s Grain for Green Program (GGP) is likely the largest centrally organized land-use change program in human history and yet its carbon sequestration benefit has yet to be systematically assessed. Here we used seven empirical/statistical equations of forest biomass carbon sequestration and five soil carbon change models to estimate the total and decadal carbon sequestration potentials of the GGP during 1999–2050, including changes in four carbon pools: aboveground biomass, roots, forest floor and soil organic carbon. The results showed that the total carbon stock in the GGP-affected areas was 682 Tg C in 2010 and the accumulative carbon sink estimates induced by the GGP would be 1697, 2635, 3438 and 4115 Tg C for 2020, 2030, 2040 and 2050, respectively. Overall, the carbon sequestration capacity of the GGP can offset about 3%–5% of China’s annual carbon emissions (calculated using 2010 emissions) and about 1% of the global carbon emissions. Afforestation by the GGP contributed about 25% of biomass carbon sinks in global carbon sequestration in 2000–2010. The results suggest that large-scale ecological restoration programs such as afforestation and reforestation could help to enhance global carbon sinks, which may shed new light on the carbon sequestration benefits of such programs in China and also in other regions.     

Climate change impacts on ecosystems and the terrestrial carbon sink: a new assessment

Climate output from the UK Hadley Centre's HadCM2 and HadCM3 experiments for the period 1860 to 2100, with IS92a greenhouse gas forcing, together with predicted patterns of N deposition and increasing CO₂, were input (offline) to the dynamic vegetation model, Hybrid v4.1 (Friend et al., 1997; Friend and White, 1999). This model represents biogeochemical, biophysical and biogeographical processes, coupling the carbon, nitrogen and water cycles on a sub-daily timestep, simulating potential vegetation and transient changes in annual growth and competition between eight generalized plant types in response to climate.Global vegetation carbon was predicted to rise from about 600 to 800 PgC (or to 650 PgC for HadCM3) while the soil carbon pool of about 1100 PgC decreased by about 8%. By the 2080s, climate change caused a partial loss of Amazonian rainforest, C₄ grasslands and temperate forest in areas of southern Europe and eastern USA, but an expansion in the boreal forest area. These changes were accompanied by a decrease in net primary productivity (NPP) of vegetation in many tropical areas, southern Europe and eastern USA (in response to warming and a decrease in rainfall), but an increase in NPP of boreal forests. Global NPP increased from 45 to 50 PgC y⁻¹ in the 1990s to about 65 PgC y⁻¹ in the 2080s (about 58 PgC y⁻¹ for HadCM3). Global net ecosystem productivity (NEP) increased from about 1.3 PgC y⁻¹ in the 1990s to about 3.6 PgC y⁻¹ in the 2030s and then declined to zero by 2100 owing to a loss of carbon from declining forests in the tropics and at warm temperate latitudes — despite strengthening of the carbon sink at northern high latitudes. HadCM3 gave a more erratic temporal evolution of NEP than HadCM2, with a dramatic collapse in NEP in the 2050s.