Acid neutralization of precipitation in Northern China

There is an increasing concern over the impact of human-related emissions on the acid precipitation in China. However, few measurements have been conducted so far to clarify the acid-neutralization of precipitation on a regional scale. Under a network of 10 sites across Northern China operated during a 3-year period from December 2007 to November 2010, a total of 1118 rain and snow samples were collected. Of this total, 28% was acid precipitation with pH < 5.6. Out of these acid samples, 53% were found heavily acidic with pH value below 5.0, indicating significantly high levels of acidification of precipitation. Most of the acidity of precipitation was caused by H2SO4 and HNO3, their relative contribution being 72% and 28%, respectively. However; the contribution of HNO3 to precipitation acidity will be enhanced due to the increasing NO(x) and stable SO2 emissions in future. Neutralization factors for K+, NH4+, Ca2+, Na+, and Mg2+ were estimated as 0.06, 0.71, 0.72, 0.15, and 0.13, respectively. The application of multiple regression analysis further quantified higher NH4+ and Ca2+ contribution to the neutralization process, but the dominant neutralizing agent varied from site to site. The neutralization was less pronounced in the rural than urban areas, probably due to different levels of alkaline species, which strongly buffered the acidity. Presence of high concentrations of basic ions was mainly responsible for high pH of precipitation with annual volume-weighted mean (VWM) values larger than 5.6 at several sites. It was estimated that in the absence of buffering ions, for the given concentration of SO4(2-) and NO3-, the annual VWM pH of precipitation would have been recorded around 3.5 across Northern China. This feature suggested that emissions of particles and gaseous NH3 played very important role in controlling the spatial variations of pH of precipitation in the target areas.     

Wet precipitation chemistry at a high-altitude site (3,326 m a.s.l.) in the southeastern Tibetan Plateau

This paper presents the results of wet precipitation chemistry from September 2009 to August 2010 at a high-altitude forest site in the southeastern Tibetan Plateau (TP). The alkaline wet precipitation, with pH ranging from 6.25 to 9.27, was attributed to the neutralization of dust in the atmosphere. Wet deposition levels of major ions and trace elements were generally comparable with other alpine and remote sites around the world. However, the apparently greater contents/fluxes of trace elements (V, Co, Ni, Cu, Zn, and Cd), compared to those in central and southern TP and pristine sites of the world, reflected potential anthropogenic disturbances. The almost equal mole concentrations and perfect linear relationships of Na⁺ and Cl^? suggested significant sea-salts sources, and was confirmed by calculating diverse sources. Crust mineral dust was responsible for a minor fraction of the chemical components (less than 15 %) except Al and Fe, while most species (without Na⁺, Cl^?, Mg²⁺, Al, and Fe) arose mainly from anthropogenic activities. High values of as-K⁺ (anthropogenic sources potassium), as-SO₄ ^2?, and as-NO₃ ^? observed in winter and spring demonstrated the great effects of biomass burning and fossil fuel combustion in these seasons, which coincided with haze layer outburst in South Asia. Atmospheric circulation exerted significant influences on the chemical components in wet deposition. Marine air masses mainly originating from the Bay of Bengal provided a large number of sea salts to the chemical composition, while trace elements during summer monsoon seasons were greatly affected by industrial emissions from South Asia. The flux of wet deposition was 1.12 kg?N?ha^?1?year^?1 for NH₄ ⁺–N and 0.29 kg?N?ha^?1?year^?1 for NO₃ ^?–N. The total atmospheric deposition of N was estimated to be 6.41 kg?N?ha^?1?year^?1, implying potential impacts on the alpine ecosystem in this region.     

Rainfall acidity as related to meteorological parameters in Northern Quebec

Summer-time rainfalls during 1980 and 1981 were collected at several sites near La Grande, 200 km inland from the James Bay coast, in Northern Quebec. These were analyzed for pH and the concentrations of major ions. Concurrent and prior measurements were also taken or derived for a series of meteorological parameters including 85 Kp level wind speed and direction, 85 Kp level air temperature, vertical air movement, these during and prior to rainfall, precipitation amount, duration and intensity, prior duration of precipitation, precipitation type, boundary layer height, surface pressure and surface pressure change and atmospheric divergence.Results demonstrate that wind speed at 85 Kp level 48–72 h prior to rainfall, wind direction at 85 Kp 72 h prior, air temperature at 85 Kp during rainfall and 60–72 h prior, vertical movement of the atmosphere 24 h prior, boundary layer height, surface pressure and surface pressure change and rainfall amount and duration at the site as well as prior duration of rainfall consistently correlate with the log₁₀ of major ions in rainfall. Also surface wind direction, precipitation type and the trajectory of air masses do not consistently relate to the pH of rainfall.     

Lead isotopes in rainfall collected by a sequential sampler in suburban Tokyo

Sequential rainfall collections were obtained with a 1-mm precipitation interval at a suburban site in Tokyo. The lead–isotope composition of each fraction was precisely determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The results showed that lead isotopes clearly changed during a single rainfall event for all rainfall events investigated, and large variations were observed for three specific events. In these three events, the values of the lead isotopes in the initial stage of rainfall (wash-out stage) were similar to the so-called common lead. As precipitation proceeded, the lead isotopes tended to be more radiogenic, and in the later stage (rain-out stage) they were highly radiogenic (up to ^{206, 207, 208}Pb/²⁰⁴Pb=29.26, 26.03, and 63.64, respectively). The source of lead in the rain-out stage completely differed from that in the wash-out stage for these events. A simple mixing model with two end members (rain-out lead and wash-out lead) could explain the isotopic variations. Preliminary trajectory analysis indicated that the highly radiogenic lead was emitted and transported from South-West China. Coal combustion could be a candidate for rain-out stage lead by a selective emission of radiogenic isotopes (²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb). A selective emission mechanism is discussed. The origin of the wash-out lead may have been local and derived from a mixture of urban particulates, e.g., particles from automobile exhaust, city incinerators, roadside dust, and factory exhaust.     

Number size distribution of atmospheric aerosols during ACE-Asia dust and precipitation events

Measurements of size-resolved particle number concentrations during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) field campaign were made at the Gosan super-site, South Korea. In East Asia, dust and precipitation phenomena play a crucial role in atmospheric environment and climate studies because they are major sources and sinks of atmospheric aerosols, especially in the springtime. Total Ozone Mapping Spectrometer (TOMS) Aerosol Index and backward trajectories are analyzed to investigate the spatial and temporal evolution of dust storms. The size distributions between dust and non-dust periods and times with and without precipitation are compared. In order to understand the temporal evolution of the aerosol size distribution during dust and precipitation events, a simple aerosol dynamics model is employed. The model predicted and observed size distributions are compared with the measured data. The results show that the coarse mode particle number concentrations increase by a factor of 10–16 during dust events. During precipitation, however, particles in the coarse mode are scavenged by impaction mechanism. It is found that the larger particles are more efficiently scavenged. The degree of scavenged particle varies depending on the rainfall rate, raindrop size distribution and aerosol size distribution.     

Assessing decadal changes in rainwater alkalinity at a rural Mediterranean site in the Montseny Mountains (NE Spain)

Annual volume-weighted mean (VWM) concentrations in rainwater collected at La Castanya (LC, Montseny Mountains, NE Spain) were analysed from 1983 to 2000 to study the temporal trends in precipitation chemistry, and the causes behind the changes. A significant positive correlation was found between annual rainwater SO₄²⁻ concentrations at LC and Spanish SO₂ emissions (r=0.73, P=0.0008) both decreasing remarkably during this period. Rainwater alkalinity increased during the period, shifting from negative values at the beginning (VWM in the 5 initial years=−2.7 μeq l⁻¹) to alkaline values in recent years (VWM in the 5 final years=18.0 μeq l⁻¹). Stepwise regression analysis indicated that 88% of the variation of alkalinity could be accounted for by the variability of non-marine Ca²⁺ and non-marine SO₄²⁻, with a more prominent dependence on Ca²⁺.Rains of African provenance were highly enriched in alkalinity and Ca²⁺, but no significant increases in their occurrence were found for the study period. Because of the reported higher dust updraft in northern Africa during years of high North Atlantic Oscillation (NAO) index, we also explored the relationship between rainwater variables associated with an African provenance and NAO. Annual precipitation was inversely related to NAO (r=−0.61, P=0.007). The annual wet deposition of African dust-related elements showed no correlation with NAO, probably because wet deposition of these elements depends on two factors (precipitation and dust updraft) which have opposite behaviour with respect to NAO. We hypothesise that dry deposition of African dust during dry spells (not sampled in this study) might be higher during high NAO-index years.     

森林降水化学的变化特征和机理

研究并比较了湖南酸雨区韶山小集水区林内降水的化学特征，结果表明，与大气降水相比，穿冠水和地表穿透水中的富集的离子浓度除了NO3^-和Na^ 外均明显增加，到达地表的降水离子增加倍数最高达34．3倍；离子总量最高倍数为8．1倍，乔木树冠层的离子富集作用大于灌木层。韶山的大气降水、穿冠水和地表穿透水的年均pH分别为4．61、5．54和5．85。持续大量的降水对森林上空的污染物有较高的清除效果。     

Atmospheric fate of non-volatile and ionizable compounds

A modified version of the Multimedia Activity Model for Ionics MAMI, including two-layered atmosphere, air-water interface partitioning, intermittent rainfall and variable cloud coverage was developed to simulate the atmospheric fate of ten low volatility or ionizable organic chemicals. Probabilistic simulations describing the uncertainty of substance and environmental input properties were run to evaluate the impact of atmospheric parameters, ionization and air-water (or air-ice) interface enrichment.The rate of degradation and the concentration of OH radicals, the duration of dry and wet periods, and the parameters describing air-water partitioning (K_AW and temperature) and ionization (pK_a and pH) are the key parameters determining the potential for long range transport. Wet deposition is an important removal process, but its efficiency is limited, primarily by the duration of the dry period between precipitation events.Given the underlying model assumptions, the presence of clouds contributes to the higher persistence in the troposphere because of the capacity of cloud water to accumulate and transport non-volatile (e.g. 2,4-D) and surface-active chemicals (e.g. PFOA). This limits the efficiency of wet deposition from the troposphere enhancing long-range transport.     

Influence of air mass trajectories on the chemical composition of precipitation in India

Chemical composition of precipitation was measured with wet-only samplers at a rural site at Bhubaneswar in eastern India during 1997–1998. All rain events were compared with trajectories and precipitation fields from the ECMWF. The pH and ionic concentrations were found to vary systematically with the origin of air and the amount of rainfall along the trajectory. A seasonal cycle for pH was found with a monthly median pH below 5.0 during October–December. The highest monthly median concentration of Ca²⁺ was found in May with 20 μmol l⁻¹ and for SO₄²⁻ in January with 52 μmol l⁻¹. Samples with trajectories within 400 km from Bhubaneswar during the last 5 days were found to have a median pH slightly below 5.0 as an average. These samples also had the highest concentration for all measured ions, indicating large pollution sources within the region. Samples with continental origin showed a decrease of ∼70% in concentration if there had been rain during >50% of the last 5 days compared to rain during <50% of the last 5 days. High concentrations of Na⁺ and Cl⁻ were also found in continental samples. Resuspension of previously deposited sea salt is believed to be the reason. The data were compared with data from three other sites in western India and higher concentrations of almost all ions (NH₄⁺ being the exception) compared to Bhubaneswar were found at the west coast in monsoon samples.     

Effects of simulated acid rain on pollen physiology and ultrastructure in the apple

Viability, germination and tube length were investigated in pollen grains of field-grown 'Summerred' apple trees (Malus domestica Borkh) exposed to deionized water, rainfall or simulated acid rain at pH 5.6, 4.0 and 3.0. Pollen viability and germination significantly decreased with lower values of pH and with increasing number of treatments. The effects of pH 5.6 and natural rainfall were not significant. Electron microscope investigation of vegetative pollen cells of plants exposed to acid rain at pH 4.0 and 3.0 showed modified features in mitochondria, plastids and endoplasmic reticulum.     

Windblown Dust Contributes to High PM25 Concentrations

ABSTRACT

The revised National Ambient Air Quality Standards for PM include fine particulate standards based upon mass measurements of PM₂₅. It is possible in arid and semi-arid regions to observe significant coarse mode intrusion in the PM_2.5 measurement. In this work, continuous PM₁₀, PM_2.5, and PM_1.0 were measured during several windblown dust events in Spokane, WA. PM_{2 5} constituted ~30% of the PM₁₀ during the dust event days, compared with ~48% on the non-dusty days preceding the dust events. Both PM₁₀ and PM_2.5 were enhanced during the dust events. However, PM_1.0 was not enhanced during dust storms that originated within the state of Washington. During a dust storm that originated in Asia and impacted Spokane, PM_1.0 was also enhanced, although the Asian dust reached Washington during a period of stagnation and poor dispersion, so that local sources were also contributing to high particulate levels. The “intermodal” region of PM, defined as particles ranging in aerodynamic size from 1.0 to 2.5 um, was found to represent a significant fraction of PM₂₅ (~51%) during windblown dust events, compared with 28% during the non-dusty days before the dust events.     

Dust storm frequency and its relation to climate changes in Northern China during the past 1000 years

Dust storm events and their relation to climate changes in Northern China during the past 1000 years were analyzed by using different paleoclimate archives such as ice cores, tree rings, and historical documents. The results show that in the semiarid region, the temperature and precipitation series were significantly negatively correlated to the dust storm frequency on a decadal timescale. Compared with temperature changes, however, there was a closer correlation between precipitation changes and dust storm events on a centennial timescale. At this timescale, precipitation accounts for 40% of the variance of dust fall variations during the last 1700 years, inferring precipitation control on the formation of dust storms. In the western arid region, both temperature and precipitation changes are important forcing factors for the occurrence of dust storms in the region on a centennial timescale. In the eastern arid region, the relationship between dust storm events and climate changes are similar like in the semiarid region. As a result, the effects of climate change on dust storm events were manifested on decadal and centennial timescales during the last millennium. However, there is a phase shift in the relation between climate change and the dust storm frequency. A 1400 years reconstruction of the strength of the Siberian High reveals that long-term variations of spring Siberian High intensity might provide a background for the dynamic conditions for the frequency of historical dust storm events in Northern China.     

Characteristics of the event mean concentration (EMC) from rainfall runoff on an urban highway

The purpose of this study was to investigate the characterization of the event mean concentration (EMC) of runoff during heavy precipitation events on highways. Highway runoff quality data were collected from the 7th highway, in South Korea during 2007-2009. The samples were analyzed for runoff quantity and quality parameters such as COD_cr, TSS, TPHs, TKN, NO₃, TP, PO₄ and six heavy metals, e.g., As, Cu, Cd, Ni, Pb and Zn. Analysis of resulting hydrographs and pollutant graphs indicates that the peak of the pollutant concentrations in runoff occurs 20 min after the first rainfall runoff occurrence. The first flush effect depends on the preceding dry period and the rainfall intensity. The results of this study can be used as a reference for water quality management of urban highways.     

Dust build-up on surfaces in the indoor environment

The concentration and the composition of dust in the indoor environment has been associated with reported symptoms of the sick building syndrome. Levels of airborne concentrations of dust particles are well known. However, the relation to dust on surfaces for office environments are not well described. In this study, 662 measurements were performed of surface dust concentrations on hard surfaces in 19 buildings within Harvard University based on a sticking gelatine foil method. The measure is the dust covered area of the surface as a percentage. In three offices, the build-up of dust on surfaces was measured for a period of five days. Close to these surfaces the airborne PM_2.5 and PM₁₀ particle mass concentrations were measured simultanously. A significant correlation between the dust build-up and the difference between the PM₁₀ and the PM_2.5 was established. The particle size distribution was measured by means of an Aerodynamic Particle Sizer. The mean dust build-up normalized with the measured PM₁₀ was approximately four times higher than the equivalent calculated by a deposition model. This may in part be due to the effect of preferred orientation when particles settle to a surface. Different data for dust on surfaces and airborne particles in offices were compared. The levels of airborne particles in offices in Europe seem to be higher than the levels in the US.     

Field evaluation of an acid rain-drought stress interaction

Various methods have been proposed to simulate natural field conditions for growing agricultural crops while controlling conditions to study specific environmental effects. This report briefly describes the use of moveable rain exclusion shelters (10.4 x 40.9 m) to study the results of the interaction of acid rain and drought stress on corn and soybean yields. The rain exclusion shelters are constructed of galvanized pipe framing and covered with polyethylene film. Movement is automated by a rain switch to protect crops from ambient rainfall and to treat them with simulated acid rain The facility simulates a real environment with respect to variables such as solar exposure, wind movement, dew formation, and insect exposure, while allowing careful control of moisture regimes. Soybeans and corn were treated with average rainfall amounts, and with one-half and one-quarter of these rainfall amounts (drought stress) at two levels of rainfall acidity, pH 5.6 and 3.0. While drought stress resulted in considerable yield reduction for Amsoy and Williams soybeans, no additional reduction in yield was observed with rainfall of pH 3.0, as compared to rainfall of approximately pH 5.6. Similar results were observed for one corn cultivar, Pioneer 3377. For one year of the study however, yield of B73 x Mo17 (corn) was reduced 3139 kg ha(-1) by the most severe drought, and an additional 1883 kg ha(-1) by acid rain of pH 3.0, as compared to the control (pH 5.6). Yield reduction from acidic rain was considerably less at full water rates, resulting in a significant pH by drought stress interaction. However, during the second year of the experiment, no pH effect or drought by pH interaction was observed for this cultivar. The reason for the difference in the two years was not identified.     

Investigation into atmospheric deposition through precipitation studies at New Delhi (India)

Rain water samples were collected during the monsoon of 1994, using automatic wet-only and manual bulk collectors at a height of 30 m above the ground at the National Physical Laboratory, New Delhi. The average pH of the rain water was 5.7 and its chemical composition was dominated by NH₄ and SO₄. The free acidity of the rain water was found to be due to S04 rather than N03 and it was mainly neutralized by NH₄ and Ca. Calculation of sea salt fraction and enrichment factor revealed that this site is free for marine influence. On an average the bulk samples had 13% higher concentration than that of wet-only samples which may be due to the deposition of soil-derived particles during the 24 h period of exposure. The higher neutralization factors of Ca and Mg in bulk samples and highest dry deposition rates for Ca in comparison to other components, indicated the positive interference of dust particles in neutralization.     

Application of neutral electrolyzed water spray for reducing dust levels in a layer breeding house

Reducing airborne dust is an essential process for improving hen housing environment. Dust reduction effects of neutral electrolyzed water (pH 8.2) spray were investigated in a commercial tunnel-ventilated layer breeding house during production in northern China. A multipoint sampler was used to measure airborne dust concentration to study the dust reduction effects and distribution in the house. Compared with the control treatment (without spray), airborne dust level was reduced 34% in the 3 hr after spraying 216 mL m^?2 neutral electrolyzed water in the breeding house. The dust concentration was significantly higher during the periods of feed distribution (1.13 ± 0.13 mg m^?3) and artificial insemination (0.72 ± 0.13 mg m^?3) compared with after spray (0.47 ± 0.09 mg m^?3) and during lights-off period (0.29 ± 0.08 mg m^?3) in the three consecutive testing days (P < 0.05). The experimental cage area was divided into four zones along the length of the house, with zone 1 nearest to the evaporative cooling pad and zone 4 nearest to the fans. The air temperature, relative humidity, airflow rate, and dust concentration were measured at the sampling points of the four zones in 3 consecutive days and mortality of the birds for the duration of a month were investigated. The results showed that the air temperature, airflow rate, dust concentration, and number of dead birds increase from zone 1 to zone 4 in the tunnel-ventilated layer breeding house.

Implications: It is difficult to effectively reduce hen house airborne dust levels and limited information is available on airborne dust distribution in tunnel-ventilated hen houses. This work investigates (i) the application of neutral electrolyzed water spray for reducing dust in a layer breeding houses; (ii) dust concentration variations in 24-hr house operation; as well as (iii) the effects of location on dust concentrations. It was demonstrated that neutral electrolyzed water spray can be efficiently used for dust reduction in poultry houses. Further, a better understanding of the dust concentration variations in 24-hr house operation and in different spatial zones can contribute to bird housing environment management and poultry house design so as to improve bird health.     

Chemical composition and seasonal variation of acid deposition in Guangzhou, South China: comparison with precipitation in other major Chinese cities

With the aim of understanding the origin of acid rains in South China, we analyzed rainwaters collected from Guangzhou, China, between March 2005 and February 2006. The pH of rainwater collected during the monitoring period varied from 4.22 to 5.87; acid rain represented about 94% of total precipitation during this period. The rainwater was characterized by high concentrations of SO₄²⁻, NO₃⁻, Ca²⁺, and NH₄⁺. SO₄²⁻ and NO₃⁻, the main precursors of acid rain, were related to the combustion of coal and fertilizer use/traffic emissions, respectively. Ca²⁺ and NH₄⁺ act as neutralizers of acid, accounting for the decoupling between high SO₄²⁻ concentrations and relatively high pH in the Guangzhou precipitation. The acid rain in Guangzhou is most pronounced during spring and summer. A comparison with acid precipitation in other Chinese cities reveals a decreasing neutralization capacity from north to south, probably related to the role and origin of alkaline bases in precipitation.     

Parameterization of wet deposition of sulfate by precipitation rate

A method for the estimation of wet deposition of sulfate is developed using routinely available meteorological data and the observed airborne sulfate concentration. This approach takes into account different mechanisms of precipitation formation that determine sulfate concentration in precipitation water. Four different precipitating cloud types, including cold cloud, warm cloud, stratified layered cloud and convective cloud, according to their precipitation formations are incorporated differently to estimate sulfate concentration in precipitation water. This method is implemented to estimate wet deposition of sulfate in Seoul for the days when the airborne sulfate concentration is available. The estimated wet deposition of sulfate shows that the model slightly overestimates the wet deposition of sulfate especially for the warm cloud case while it does underestimate sulfate deposition for the Bergeron process in developing precipitation particularly when the input airborne sulfate concentration is small. The precipitation amount weighted mean wet deposition of sulfate obtained from the model, overestimates that observed by a factor of 1.6 for this case study. This discrepancy might be associated with non-steady revolutional features of precipitating clouds and the resolvable scaling difference between the model and observation.     

Chemical and strontium isotope characterization of rainwater in karst virgin forest,Southwest China

Strontium isotope ratios and concentrations of Ca²⁺, NH₄⁺, Na⁺, K⁺, Mg²⁺, Cl^?, SO₄^2?, NO₃^? and Al³⁺, Sr²⁺ were measured for 52 rainwater samples collected in virgin forest in a rural region between May 2007 and Dec. 2008. The rainwater pH values vary from 4.1 to 7.2 with a volume weight mean (VWM) value of 5.40. 40 of 52 samples have pH value above 5.0, indicating that the regional rainwater was not acidic. Among anions and cations, sulphate concentration (40.4 μeq l^?1, VWM) is the highest in the rainwater, followed by ammonium and calcium (30.2 and 20.8 μeq l^?1, VWM). Rainwater quality is characterized by low salinity and neutralized pH.The chemical compositions and ⁸⁷Sr/⁸⁶Sr ratios of the rainwater samples vary considerably. Using Na⁺ concentration as an indicator of marine origin, the proportions of sea salt and crustal elements were estimated from elemental ratios. The ⁸⁷Sr/⁸⁶Sr ratios were used to characterize different sources base on the data sets of this study and those from literatures. Such sources include weathering of limestone (⁸⁷Sr/⁸⁶Sr = 0.7075), remote soil dust (⁸⁷Sr/⁸⁶Sr > 0.7135) and anthropogenic source (fertilizers: ⁸⁷Sr/⁸⁶Sr = 0.7079). The results of the present study suggest that one likely source for high ammonium and calcium concentration is local soil. Due to a large contribution of these cations to the sulphate neutralization action, the rainwater in this region displays non-acidity, and thus has not significant environmental impact. The wet precipitation in the karst virgin forest in Guizhou province is strongly influenced by natural sources rather than anthropogenic sources.