Chemical characteristics of precipitation at metropolitan Newark in the US East Coast

To investigate the chemical characteristics of precipitation in the polluted coastal atmosphere, a total of 46 event-based precipitation samples were collected using a wet-only automatic precipitation collector from September 2006 to October 2007 at metropolitan Newark, New Jersey in the US East Coast. Samples were analyzed by ion chromatography for the concentrations of major inorganic ions (Cl⁻, NO₃⁻, SO₄²⁻, F⁻, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺) and organic acid species (CH₃COO⁻, HCOO⁻, CH₂(COO)₂²⁻, C₂O₄²⁻). Selected trace metals (Sb, Pb, Al, V, Fe, Cr, Co, Ni, Cu, Zn, Cd) in samples were determined by ICPMS. Mass concentration results show that SO₄²⁻ was the most dominant anion accounting for 51% of the total anions, controlling the acidity of the precipitation. NH₄⁺ accounted for 48.6% of the total cations, dominating the precipitation neutralization. CH₃COO⁻ and HCOO⁻ were the two dominant water-soluble organic acid species, accounting for 42% and 40% of the total organic acids analyzed, respectively. Al, Zn and Fe were the three major trace metals in precipitation, accounting for 34%, 27%, and 25% of the total mass of metals analyzed. The pH values in precipitation ranged from 4.4 to 4.9, indicating an acidic nature. Enrichment Factor (EF) Analysis showed that Na⁺, Cl⁻, Mg²⁺ and K⁺ in the precipitation were primarily of marine origin, while most of the Fe, Co and Al were from crust sources. Pb, V, Cr, Ni were moderately enriched with EFs ranging 43–410, while Zn, Sb, Cu, Cd and F⁻ were highly enriched with EFs > 700, indicating significant anthropogenic influences. Factor analysis suggests 6 major sources contributing to the observed composition of precipitation at this location: (1) nitrogen-enriched soil, (2) secondary pollution processes, (3) marine sources, (4) incinerations, (5) oil combustions, and (6) malonate–vanadium enriched sources. To further explore the source–precipitation event relationships and seasonality, cluster analysis was performed for all precipitation events. Results show that about half of the precipitation events were characterized by mixed sources. Significant influences of nitrogen-enriched soil and marine sources were associated with precipitation events in spring and autumn, while secondary pollution processes, incineration and oil combustion contributed greatly in summer.     

Chemical composition of rainwater in the northeastern Romania, Iasi region (2003–2006)

Chemical composition of rainwater was studied in the northeastern Romania, Iasi region, and the concentrations of major inorganic and organic ions were measured in samples collected between April 2003 and December 2006. The pH of the rainwater is 5.92 (volume weighted mean average, VWM) suggesting a sufficient load of alkaline components neutralizing its acidity. On average, 97% of the acidity in the collected samples is neutralized by CaCO₃ and NH₃. Clear seasonal variations were observed for some of the identified ions (e.g., SO₄²⁻, NO₃⁻, Ca²⁺, NH₄⁺). The data obtained during this work revealed that both concentrations and fluxes of anthropogenic source-related ions (e.g., SO₄²⁻, NO₃⁻ and NH₄⁺) are among the highest reported for European sites. It is shown that meteorology and long-range transport processes may concur to their high levels.     

Quality of roof runoff waters from an urban region (Gda sk, Poland)

The paper presents the results of testing of roof runoff waters from buildings in the city of Gda sk (Poland), carried out as a part of a broader research project aimed at the determination of pollutant levels in precipitation. The analytes determined included volatile organohalogen compounds, petroleum hydrocarbons, Na⁺, K⁺, NH₄⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₂⁻, NO₃⁻, PO₄³⁻, SO₄²⁻ ions, as well as organonitrogen, organophosphorus and organochlorine pesticides. In addition, the toxicity and pH of the samples were examined. The samples were collected over a period of six months, during or immediately following precipitation events. More than half of the samples (25) were found to be toxic, with inhibition exceeding 20%. The toxicity was weakly correlated to the levels of organonitrogen and organophosphorus pesticides in runoff waters. It was established that at least in some cases the roofing material affected the levels of the pollutants found in the samples.     

The contribution of dry deposited ammonia and sulphur dioxide to the composition of precipitation from continuously open gauges

A series of experiments using bulk precipitation collectors of the type used in the UK precipitation chemistry network measured the amounts of NH₄⁺, SO₄²⁻ and other ions that could be washed from funnels (diameter 15 cm) exposed to a wide range of NH₃ and SO₂ concentrations over periods from hours to days. In dry conditions, the average deposition flux of NH₃ was between 50 and 120 nmol NH₄⁺ funnel⁻¹ d⁻¹ (0.1–0.3 kg N ha⁻¹ yr⁻¹), and was independent of the concentration of NH₃. Dry deposition of NH₃ to wet funnels at small NH₃ concentrations was almost 5 times that to dry funnels under the same conditions (average 240 nmol funnel⁻¹ d⁻¹; 0.7 kg ha⁻¹ yr⁻¹), and increased with increasing NH₃ concentrations. The amount of NH₄⁺ ions remaining on the funnel surface was inversely proportional to the vapour pressure deficit during the experiment. This result was interpreted as a dependence on the duration of surface wetness, with greater deposition of NH₄⁺ when evaporation rates of surface water were small.The amount of SO₂ deposited on funnel surfaces was closely related to the amount of NH₃ deposited, in both wet and dry conditions, but was not strongly correlated with the SO₂ concentration. At low NH₃ and SO₂ concentrations the average deposition to dry funnels was 70 nmol SO₄²⁻ funnel⁻¹ d⁻¹ (0.5 kg ha⁻¹ yr⁻¹), and to wet funnels was approximately 2.5 times larger. The results are interpreted in terms of the balance between the rate of evaporation of surface water, and the rate of oxidation of SO₂, which leads to the ‘fixing’ of NH₄⁺ ions on the surface as involatile salts.It is predicted that dry deposition of NH₃ to funnel surfaces across the UK Secondary Network could account for as much as one-half of the measured bulk wet deposition at sites where wet deposition of NH₄–N is small. The amount of dry deposition depends on how long and how often funnel surfaces are wetted by rain or dew, and on the air concentrations of NH₃. These predictions are based on funnels being wetted only once per day. More frequent wetting would increase the contribution from dry deposition, and the consequent overestimate of wet deposition of NH₄–N across the UK by using data obtained from bulk collectors. To some extent this overestimate may be offset by microbial degradation and loss of NH₄–N in weekly bulk precipitation samples during collection and storage.     

Atmospheric deposition and canopy exchange processes in alpine forest ecosystems (northern Italy)

Throughfall and bulk precipitation chemistry were studied for five years (June 1994–May 1999) at two high elevation forest sites (Val Gerola and Val Masino) which were known to differ in terms of tree health, as assessed by live crown condition. The ion concentration of bulk precipitation samples did not differ significantly between sites, except for Mg²⁺, while the throughfall concentrations differed in the measured values of H⁺, N-NO₃⁻, Cl⁻, Na⁺, K⁺, DOC and weak organic acids. The results of the application of the canopy exchange model indicated a higher contribution from the dry deposition of N-NO₃⁻, N-NH₄⁺ and H⁺ at Val Gerola, where the damage symptoms were more evident. In addition, the canopy leaching of Ca²⁺, K⁺ and weak organic acids were 47%, 21% and 27% higher at Val Gerola than at Val Masino. Annual SO₄²⁻ deposition fluxes (21.3 kg ha⁻¹ yr⁻¹ at Val Masino and 23.6 kg ha⁻¹ yr⁻¹ at Val Gerola) were similar to those reported for moderately polluted European and U.S. sites. Annual N loads were 13.6 and 13.1 kg ha⁻¹ yr⁻¹ in the bulk input, and 15.0 and 18.0 kg ha⁻¹ yr⁻¹ in throughfall inputs, at Val Masino and Val Gerola, respectively. The contribution of the organic fraction to the total N atmospheric deposition load is significant, constituting 17% of the bulk flux and 40% of the throughfall flux. Measured nitrogen loads exceed the critical nutrient loads by several kg N ha⁻¹ at both stations. In particular the nitrogen throughfall load at Val Gerola was about 3 times higher than the critical values.     

Spatial distribution and source identification of wet deposition at remote EANET sites in Japan

Wet deposition of major ions was discussed from the viewpoint of its potential sources for six remote EANET sites in Japan (Rishiri, Happo, Oki, Ogasawara, Yusuhara, and Hedo) having sufficiently high data completeness during 2000–2004. The annual deposition for each site ranged from 12.1 to 46.6 meq m⁻² yr⁻¹ for nss-SO₄²⁻, from 5.0 to 21.9 meq m⁻² yr⁻¹ for NO₃⁻. The ranges of annual deposition of the two ions for the sites were lower than those for urban and rural sites in Japanese Acid Deposition Survey by Ministry of the Environment, Japan, and higher than those for global remote marine sites. Factor analysis was performed on log-transformed daily wet deposition of major ions for each site. The obtained two factors were interpreted as (1) acid and soil source (or acid source for some sites), and (2) sea-salt source for all the sites. This indicates that wet deposition of ions over the remote areas in Japan has a similar structure in terms of types of sources. Factor scores of acid and soil source were relatively high during Kosa (Asian dust) events in spring in western Japan. Back-trajectories for high-deposition episodes of acid and soil source (or acid source) for the remote sites showed that episodic air masses frequently came from the northeastern area of Asian Continent in spring and winter, and from central China in summer and autumn. This indicates a large contribution of continental emissions to wet deposition of ions over the remote areas in Japan.     

Recent trends in chemical composition of bulk precipitation at Estonian monitoring stations 1994–2001

Monthly and annual means of main anions (SO₄²⁻, NO₃⁻, Cl⁻) and summed base cations (Ca²⁺, Mg²⁺, K⁺, Na⁺) in bulk precipitation were studied at 10 stations during an 8-year monitoring period. The data showed statistically significant decreasing trends in most cases. Average declines of mean annual volume-weighted concentrations for both anions and cations were about two-fold. Despite the decrease, the loads of S and cations are still relatively high in Estonia (about 4–14 kg S ha⁻¹ and 0.6–1.2 keq ha⁻¹, respectively) compared with the loads in Finland and Sweden. Estimated linear decline trends followed the same pattern as annually combusted oil shale from Estonian power plants and emissions of SO₂ and fly ash. Recent trends in chemical composition of bulk precipitation at the monitoring stations reflected economic changes in Estonia as well as transboundary fluxes from neighbouring countries.     

Natural and anthropogenic factors affecting the groundwater quality in the Nandong karst underground river system in Yunan, China

The Nandong Underground River System (NURS) is located in a typical karst agriculture dominated area in the southeast Yunnan Province, China. Groundwater plays an important role for social and economical development in the area. However, with the rapid increase in population and expansion of farm land, groundwater quality has degraded. 42 groundwater samples collected from springs in the NURS showed great variation of chemical compositions across the study basin. With increased anthropogenic contamination in the area, the groundwater chemistry has changed from the typical Ca–HCO₃ or Ca (Mg)–HCO₃ type in karst groundwater to the Ca–Cl (+ NO₃) or Ca (Mg)–Cl (+ NO₃), and Ca–Cl (+ NO₃ + SO₄) or Ca (Mg)–Cl (+ NO₃ + SO₄) type, indicating increases in NO₃⁻, Cl⁻ and SO₄²⁻ concentrations that were caused most likely by human activities in the region. This study implemented the R-mode factor analysis to investigate the chemical characteristics of groundwater and to distinguish the natural and anthropogenic processes affecting groundwater quality in the system. The R-mode factor analysis together with geology and land uses revealed that: (a) contamination from human activities such as sewage effluents and agricultural fertilizers; (b) water–rock interaction in the limestone-dominated system; and (c) water–rock interaction in the dolomite-dominated system were the three major factors contributing to groundwater quality. Natural dissolution of carbonate rock (water–rock interaction) was the primary source of Ca²⁺ and HCO₃⁻ in groundwater, water–rock interaction in dolomite-dominated system resulted in higher Mg²⁺ in the groundwater, and human activities were likely others sources. Sewage effluents and fertilizers could be the main contributor of Cl⁻, NO₃⁻, SO₄²⁻, Na⁺ and K⁺ to the groundwater system in the area. This study suggested that both natural and anthropogenic processes contributed to chemical composition of groundwater in the NURS, human activities played the most important role, however.     

PM composition and source reconciliation in Mexico City

PM_2.5 and PM₁₀ were collected during 24-h sampling intervals from March 1st to 31st, 2006 during the MILAGRO campaign carried out in Mexico City's northern region, in order to determine their chemical composition, oxidative activity and the estimation of the source contributions during the sampling period by means of the chemical mass balance (CMB) receptor model. PM_2.5 concentrations ranged from 32 to 70 μg m⁻³ while that of PM10 did so from 51 to 132 μg m⁻³. The most abundant chemical species for both PM fractions were: OC, EC, SO₄²⁻, NO₃⁻, NH₄⁺, Si, Fe and Ca. The majority of the PM mass was comprised of carbon, up to about 52% and 30% of the PM2.5 and PM10, respectively. PM2.5 constituted more than 50% of PM10. The redox activity, assessed by the dithiothreitol (DTT) assay, was greater for PM_2.5 than for PM₁₀, and did not display significant differences during the sampling period. The PM_2.5 source reconciliation showed that in average, vehicle exhaust emissions were its most important source in an urban site with a 42% contribution, followed by re-suspended dust with 26%, secondary inorganic aerosols with 11%, and industrial emissions and food cooking with 10% each. These results had a good agreement with the Emission Inventory. In average, the greater mass concentration occurred during O₃S that corresponds to a wind shift initially with transport to the South but moving back to the North. Taken together these results show that PM chemical composition, oxidative potential, and source contribution is influenced by the meteorological conditions.     

Real-time wet scavenging of major chemical constituents of aerosols and role of rain intensity in Indian region

Real-time simultaneous studies on chemical characteristics of rainwater and PM₁₀ aerosols were carried out to understand the scavenging of major chemical components in Indian region. The concentrations of Ca²⁺, NH₄⁺, SO₄²⁻ and NO₃⁻ were observed to be lower in the aerosol samples collected during rain as compared to before and after rain events. The most significant reduction was noticed for Ca²⁺ (74%) during rain which showed highest scavenging ratio (SR) and indicated that below-cloud scavenging is an effective removal process for Ca²⁺ in Indian region. Among non-sea salt components, Ca²⁺ had highest SR at Hyderabad indicating typical characteristics of crustal influence as abundance of calcium carbonate in soil dust has been reported in India. However, the levels of these major chemical components gradually got build-up in due course of time. After rain events, the levels of SO₄²⁻ aerosols were noticed to be substantially higher (more than double) within 24 h. In general, scavenging ratios for all components (except Ca²⁺, NH₄⁺ and K⁺) were higher over BOB as compared to Hyderabad. The maximum fall in aerosol levels (BR minus AR) was observed during continuous and low intensity rain events that did not allow building up of aerosol concentrations.     

Temporal and spatial relationships in fine particle strong acidity, sulphate, PM1O, and PM2.5 across multiple canadian locations

The Canadian Acid Aerosol Measurement Program (CAAMP) was established in 1992 to gain a better understanding of the atmospheric behaviour of fine particle strong acidity (“acid aerosols”) and to facilitate an assessment of the potential health risks associated with acid aerosols and particles in general. During 1992. 1993 and 1994, annular denuder and filter measurements were taken at four sites in Ontario, two in Quebec, three in the Atlantic Provinces and one in the greater Vancouver area. Mean fine particle sulphate concentrations (SO₄²⁻) were highest in southern Ontario (annual average ranged from 40–70 nmol m⁻³), lowest at a site in the Vancouver area (average = 16 nmol m⁻³) and second lowest in rural Nova Scotia. However, mean fine particle strong acid concentrations (H⁺) were geographically different. The highest mean concentrations were at the east coast sites (annual average of up to 30 nmol m⁻³). Acidities were lower in areas where the fine particle acidity experienced greater neutralization from reaction with ammonia. This included the major urban centres (i.e. Toronto and Montréal) and areas with greater amounts of agricultural activity, as in rural southern Ontario. On average, ambient concentrations of fine and coarse particle mass were larger in the urban areas and also in areas where SO₄²⁻ levels were higher. All the particle components were episodic. However, compared to SO₄²⁻ and fine particles (PM_2.5 or PM_2.1, depending upon inlet design), episodes of H⁺ tended to be less frequent and of shorter duration, particularly in Ontario. Saint John, New Brunswick, had the highest mean annual H⁺ concentration, which was 30 nmol m⁻³. H⁺ episodes (24 h concentration > 100 nmol m⁻³) were also the most frequent at this location. The high levels in Saint John were partially due to local sulphur dioxide sources and heterogeneous chemistry occurring in fog, which, on average, led to a 50% enhancement in sulphate, relative to upwind conditions.There was a substantial amount of intersite correlation in the day to day variations in H⁺, SO₄²⁻ , PM_2.5 and PM₁₀ (fine + coarse particles) concentrations, which is due to the influence of synoptic-scale meteorology and the relatively long atmospheric lifetime of fine particles. Sulphate was the most regionally homogenous species. Pearson correlation coefficients comparing SO₄²⁻ between sites ranged from 0.6 to 0.9, depending on site separation and lag time. In many cases, particle episodes were observed to move across the entire eastern portion of Canada with about a two-day lag between the SO₄²⁻ levels in southern Ontario and in southern Nova Scotia.     

Ionic composition of precipitation at the Central Anatolia (Turkey)

Concentrations of major ions, SO₄²⁻, NO₃⁻, Cl⁻, H⁺, Ca²⁺, K⁺, Mg²⁺, Ca²⁺ and conductivity were measured in approximately 300 daily, wet-only rain samples collected at a permanent rural station between 1993 and 1998. Concentrations of anthropogenic ions NH₄⁺, SO₄²⁻ and NO₃⁻ were among the highest values reported in whole EMEP network, suggesting that the Anatolian plateau is under strong influence of distant emission sources. Although transport of pollutants have significant influence on the chemical composition of precipitation, average pH of the rainwater is 6.2 due to extensive neutralization of acidity. Approximately 95% of the acidity in collected samples is neutralized, particularly in summer season. The neutralizing agents are primarily CaCO₃ and NH₃. Concentrations of crustal ions are higher in summer season due to enhanced resuspension of soil particles from dry surface soil. Concentrations of anthropogenic ions SO₄²⁻ and NO₃⁻ do not change significantly between summer and winter due to higher intensity of rains in summer season. Although concentrations of ions measured in this study is among the highest reported in EMEP network, wet deposition fluxes are low compared to flux values reported for similar sites in Europe, due to low annual precipitation in the Anatolia. Wet deposition fluxes of all measured parameters are highly episodic. Source regions affecting chemical composition precipitation in the Central Anatolia is investigated using trajectory statistics.     

Diffusion of HTO, Cl and I in Opalinus Clay samples from Mont Terri: Effect of confining pressure

Diffusion coefficients (T=23±2 °C) and accessible porosities for HTO, ³⁶Cl⁻ and ¹²⁵I⁻ were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na⁺ and Cl⁻ as the main components (I=0.42 M).The measured values of the effective diffusion coefficients (D_e) and rock capacity factors (α) are: D_e=1.2–1.5×10⁻¹¹ m² s⁻¹ and α=0.09–0.11 for HTO, D_e=4.0–5.5×10⁻¹² m² s⁻¹ and α=0.05 for ³⁶Cl⁻ and D_e=3.2–4.6×10⁻¹² m² s⁻¹ and α=0.07–0.10 for ¹²⁵I⁻. For non-sorbing tracers (HTO, ³⁶Cl) the rock capacity factor α is equal to the diffusion-accessible porosity . The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of 17% for HTO, 28% for ³⁶Cl⁻ and 30% for ¹²⁵I⁻. Moreover, the diffusion coefficients for ³⁶Cl⁻ and ¹²⁵I⁻ are smaller than for HTO, which is consistent with an effect arising from anion exclusion.The diffusion coefficients of HTO and ¹²⁵I⁻ measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Multispecies transport of metal–EDTA complexes and chromate through undisturbed columns of weathered fractured saprolite

Laboratory-scale tracer experiments were conducted to investigate the geochemical and hydrological processes that govern the fate and transport of organically chelated radionuclides and toxic metals in undisturbed saturated columns of weathered, fractured shale saprolite. Three long-term, reactive contaminant injections were pulsed onto three separate soil columns, with the following influent mixtures: (1) ¹⁰⁹CdEDTA²⁻, (2) ¹⁰⁹CdEDTA²⁻ and ^57,58Co(II)EDTA²⁻, and (3) ¹⁰⁹CdEDTA²⁻, ⁵⁷Co(III)EDTA⁻, and H⁵¹CrO₄⁻. Both single and multiple species experiments were conducted to determine the importance of interaction between the contaminants and competition for surface sites. Flow interruption was used to identify physical and chemical non-equilibrium (PNE and CNE) which were caused by multiple pore-region flow and rate-limited chemical reactions, respectively. Reactive contaminant transport through the fractured, weathered shale was affected by sorption, redox, and dissociation reactions, which were mediated by soil organic matter and surficial oxides of Fe, Mn, and Al. The transport of CdEDTA²⁻ was significantly influenced by ligand-promoted dissolution of subsurface Fe and Al sources, resulting in the liberation of Cd²⁺, Al(III)EDTA⁻ and Fe(III)EDTA⁻. Flow interruption confirmed that the surface-mediated dissociation reaction was time-dependent, with the stability of the CdEDTA²⁻ complex dependent on its residence time within the soil. The migration of Co(II)EDTA²⁻ was dominated by oxidization to the highly stable Co(III)EDTA⁻ species, and elevated effluent Mn²⁺ suggested that surficial Mn(IV) oxides likely catalyzed the redox reaction, though Fe-oxides may have also contributed to the reaction. Dissociation (12%) of the Co(II)EDTA²⁻ complex was first observed during flow interruption, indicating that rate-limited dissociation of the complex by Fe-oxides may be significant under equilibrium conditions. The transport of HCrO₄⁻ was significantly altered by the reduction of mobile Cr(VI) to irreversibly bound Cr(III). The reduction reaction was catalyzed by surface-bound natural organic matter and flow interruption confirmed that the reaction was time-dependent. There was little evidence of competitive effects between the various contaminants in the multispecies experiments, since each was influenced by a different geochemical process during transport through the soil. The results of this study further support research findings that suggest anionic toxic metals and radionuclide–organic complexes can be significantly influenced by soil geochemical processes that can both enhance and impede the subsurface migration of these contaminants.     

Static secondary ion mass spectrometry as a new analytical tool for measuring atmospheric particles on insulating substrates

The paper presents static secondary ion mass spectrometry (S-SIMS) analyses of aerosol particles, which have been collected on an insulating polycarbonate filter (nuclepore) using a two-stage streaker sampler. A method was developed to analyze one streaker sample in its entirety without the need of cutting the filter. The latter allows the analysis of the same sample set with complementary techniques. Simultaneous detection of low Z atomic ions (Z<11) together with mean Z atomic ions (11<Z<82) and molecular fragment ions (e.g. HSO₄⁻,NO₂⁻,NH₄⁺) has shown to be feasible and has proven to be a major advantage of this technique. The large amounts of spectral data received were reduced by statistical clustering and were interpreted. A separate group of positive ions, e.g. Fe, K, Mn, Al, and Mg showed correlation with the PO₂ ion in the negative mode and were identified as particle emission from the steel plant. Practical problems of sample introduction and spectral effects due to charge compensation were solved and will be discussed. Despite the lack of quantitative analysis, static SIMS can be used to determine the relative abundance of compounds present in the sample and the correlation between them. In addition, the technique has been proven to provide complementary information to particle induced X-ray emission results of the same sample.     

High concentrations and dry deposition of reactive nitrogen species at two sites in the North China Plain

Atmospheric concentrations of major reactive nitrogen (N_r) species were quantified using passive samplers, denuders, and particulate samplers at Dongbeiwang and Quzhou, North China Plain (NCP) in a two-year study. Average concentrations of NH₃, NO₂, HNO₃, pNH₄⁺ and pNO₃⁻ were 12.0, 12.9, 0.6, 10.3, and 4.7 μg N m⁻³ across the two sites, showing different seasonal patterns of these N_r species. For example, the highest NH₃ concentration occurred in summer while NO₂ concentrations were greater in winter, both of which reflected impacts of N fertilization (summer) and coal-fueled home heating (winter). Based on measured N_r concentrations and their deposition velocities taken from the literature, annual N dry deposition was up to 55 kg N ha⁻¹. Such high concentrations and deposition rates of N_r species in the NCP indicate very serious air pollution from anthropogenic sources and significant atmospheric N input to crops.     

Exposure of acid aerosol for schoolchildren in metropolitan Taipei

Metropolitan Taipei, which is located in the subtropical area, is characterized by high population and automobile densities. For convenience, most primary schools are located near major roads. This study explores the exposure of acid aerosols for schoolchildren in areas in Taipei with different traffic densities. Acid aerosols were collected by using a honeycomb denuder filter pack sampling system (HDS). Experimental results indicated that the air pollutants were significantly correlated with traffic densities. The ambient air NO₂, SO₂, HNO₃, NO₃⁻, SO₄²⁻, and aerosol acidity concentrations were 31.3 ppb, 4.7 ppb, 1.3 ppb, 1.9 μg m⁻³, 18.5 μg m⁻³, and 49.5 nmol m⁻³ in high traffic density areas, and 6.1 ppb, 1.8 ppb, 0.9 ppb, 0.7 μg m⁻³, 8.8 μg m⁻³ and 14.7 nmol m⁻³ in low traffic density areas. The exposure levels of acid aerosols for schoolchildren would be higher than the measurements because the sampling height was 5 m above the ground. The SO₂ levels were low (0.13–8.03 ppb) in the metropolitan Taipei. However, the SO₄²⁻ concentrations were relatively high, and might be attributed to natural emissions of sulfur-rich geothermal sources. The seasonal variations of acid aerosol concentrations were also observed. The high levels of acidic particles in spring time may be attributed to the Asian dust storm and low height of the mixture layer. We conclude that automobile contributed not only the primary pollutants but also the secondary acid aerosols through the photochemical reaction. Schoolchildren were exposed to twice the acid aerosol concentrations in high traffic density areas compared to those in low traffic density areas. The incidence of allergic rhinitis of schoolchildren in the high traffic density areas was the highest in spring time. Accompanied by high temperature variation and high levels of air pollution in spring, the health risk of schoolchildren had been observed.     

Association of the mutagenicity of airborne particles with the direct emission from combustion processes investigated in Osaka, Japan

The association of the direct-acting mutagenicity of soluble organic fraction of airborne particles toward Salmonella typhimurium YG1024 strain with the direct emission was investigated at a roadside and at a residential area in Osaka, Japan. The direct-acting mutagenicity was evaluated as mutagenic activity per unit volume of ambient air (rev m⁻³) and/or that per airborne particulate weight collected on a filter (rev mg⁻¹). The annual or diurnal changes of the mutagenicity of airborne particles at the residential site showed similar patterns to those of some gaseous pollutants such as NO₂ and SO₂, which were emitted from combustion processes. This result indicates that the mutagenicity is mainly attributable to the primary emissions. From the analysis of the relationship between the wind sector and the mutagenic intensity, rev m⁻³ and rev mg⁻¹ values were strongly affected by the emissions from the fixed sources and from the mobile sources, respectively. The rev m⁻³ value and concentration of 1-nitropyrene (1-NP) in unit per m³ at the roadside were a factor of 2.6 and 2.8 higher than those at the residential site, respectively, but the rev mg⁻¹ value and concentration of 1-NP in unit per mg at the roadside were substantially comparable to those at the residential area. These observations suggest that the characteristics of the airborne particles can be attributed to the automotive emissions even at the suburban area.     

Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials

The emissions of selected flame retardants were measured in 1- and 0.02-m³ emission test chambers and 0.001-m³ emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SER_a) of TCPP varied between 20 ng m⁻² h⁻¹ and 140 μg m⁻² h⁻¹.The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SER_u) of organophosphates were determined to be 10–85 ng unit⁻¹ h⁻¹. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SER_a of between 0.2 and 6.6 ng m⁻² h⁻¹ and an SER_u of between 0.6 and 14.2 ng unit⁻¹ h⁻¹. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SER_a of between 0.1 and 29 ng m⁻² h⁻¹ and decabromodiphenylether was not detectable at all.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.