Effects of field-applied composted cattle manure and chemical fertilizer on ammonia and particulate ammonium exchanges at an upland field

The present study aimed to investigate the NH₃ volatilization loss from field-applied compost and chemical fertilizer and evaluate the atmosphere–land exchange of NH₃ and particulate NH₄⁺ (pNH₄) at an upland field with volcanic ash soil (Andosol) in Hokkaido, northern Japan. Two-step basal fertilization was conducted on the bare soil surface. First, a moderately fermented compost of cattle manure was applied by surface incorporation (mixing depth, 0–15 cm) at a rate of 117 kg N ha⁻¹ as total nitrogen (T-N) corresponding to 9.9 kg N ha⁻¹ as ammoniacal nitrogen (NH₄–N). Twelve days later, a chemical fertilizer containing 10% (w/w) of NH₄–N as a mixture of ammonium sulfate and ammonium phosphates was applied by row placement (cover depth, 3 cm) at a rate of 100 kg N ha⁻¹ as NH₄–N. The study period was divided into the first-half, beginning after the compost application (CCM period), and the second-half, beginning after the chemical fertilizer application (CF period). The mean air concentrations of NH₃ and pNH₄ (1.5 m height) were 7.6 and 3.0 μg N m⁻³, respectively, in the CCM period; the values were 3.7 and 3.9 μg N m⁻³, respectively, in the CF period. The composition ratios of NH₃ to the sum of NH₃ and pNH₄ (1.5 m height) were 72% and 49% in the CCM and CF periods, respectively. The NH₃ volatilization loss from the compost was 0.8% of the applied T-N (or 9.3% of the applied NH₄–N) and that from the chemical fertilizer was near zero. Excluding the period immediately after the compost application, the upland field acted as a net sink for NH₃ and pNH₄.     

Influence of liberated silver from silver nanoparticles on nitrification inhibition of Nitrosomonas europaea

The ecotoxicity of silver nanoparticles (Ag-NPs) to wastewater biota, including ammonia oxidizing bacteria (AOB), is gaining increasing interest as the number of products containing Ag-NPs continues to rise exponentially and they are expected to accumulate in wastewater treatment plants. This research demonstrated that the addition order of Ag-NP and the media constituents had a profound influence on the stability of the Ag-NP suspension and the corresponding repeatability of results and sensitivity of Nitrosomonas europaea. N. europaea, a model AOB, was found to be extremely sensitive to ionic silver (Ag⁺) and two sizes of Ag-NPs (20 and 80 nm). Ag⁺ exposures resulted in the highest level of toxicity with smaller Ag-NPs (20 nm) being more toxic than larger Ag-NPs (80 nm). The increased sensitivity of N. europaea to smaller Ag-NPs was caused by their higher rates of dissolved silver (dAg) release, via dissolution, due to a greater surface area to volume ratio. dAg was shown to be responsible for the vast majority of the observed Ag-NP toxicity, as determined by abiotic Ag-NP dissolution tests. For the sizes of Ag-NP studied (20 and 80 nm), there appears to be a negligible nanoparticle-specific toxicity. This was further supported by similarities in inhibition mechanisms between Ag⁺ and Ag-NP, with both causing decreases in AMO activity and destabilization of the outer-membrane of N. europaea. Finally, equal concentrations of total silver were found to be tightly associated to both Ag⁺ and Ag-NP-exposed cells despite Ag-NP concentrations being five times greater, by mass, than Ag⁺ concentrations.     

Traffic generated non-exhaust particulate emissions from concrete pavement: A mass and particle size study for two-wheelers and small cars

This study aimed to understand the non-exhaust (NE) emission of particles from wear of summer tire and concrete pavement, especially for two wheelers and small cars. A fully enclosed laboratory-scale model was fabricated to simulate road tire interaction with a facility to collect particles in different sizes. A road was cast using the M-45 concrete mixture and the centrifugal casting method. It was observed that emission of large particle non exhaust emission (LPNE) as well as PM₁₀ and PM_2.5 increased with increasing load. The LPNE was 3.5 mg tire⁻¹ km⁻¹ for a two wheeler and 6.4 mg tire⁻¹ km⁻¹ for a small car. The LPNE can lead to water pollution through water run-off from the roads. The contribution of the PM₁₀ and PM_2.5 was smaller compared to the LPNE particles (less than 0.1%). About 32 percent of particle mass of PM₁₀ was present below 1 μm. The number as well as mass size distribution for PM₁₀ was observed to be bi-modal with peaks at 0.3 μm and 4–5 μm. The NE emissions did not show any significant trend with change in tire pressure.     

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.     

Neptunium(V) adsorption to calcite

The migration behavior of the actinyl ions U(VI)O₂²⁺, Np(V)O₂⁺ and Pu(V,VI)O₂^(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO₂⁺ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO₂ partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased K_D values after desorption compared to adsorption.     

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.     

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag–Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag–PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72 h in freshwater (500–600 μg L⁻¹) and seawater (1300–1500 μg L⁻¹), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag⁺ (1.1, 400 and 0.11 μg L⁻¹, respectively), Ag–Cit (3.0, 2380 and 0.15 μg L⁻¹, respectively) and Ag–PVP (19.5, 3690 and 2.0 μg L⁻¹, respectively) varied widely, with toxicity in the order Ag⁺ > Ag–Cit > Ag–PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag⁺ or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.     

Assessment of traffic-related air pollution in the urban streets before and during the 2008 Beijing Olympic Games traffic control period

In order to investigate the air quality and the abatement of traffic-related pollution during the 2008 Olympic Games, we select 12 avenues in the urban area of Beijing to calculate the concentrations of PM₁₀, CO, NO₂ and O₃ before and during the Olympic traffic controlling days, with the OSPM model.Through comparing the modeled results with the measurement results on a representative street, the OSPM model is validated as sufficient to predict the average concentrations of these pollutants at street level, and also reflects their daily variations well, i.e. CO presents the similar double peaks as the traffic flow, PM₁₀ concentration is influenced by other sources. Meanwhile, the model predicts O₃ to stay less during the daytime and ascend in the night, just opposite to NO₂, which reveals the impact of photochemical reactions. In addition, the predicted concentrations on the windward side often exceed the leeward side, indicating the impact of the special street shape, as well as the wind.The comparison between the predicted street concentrations before and during the Olympic traffic control period shows that the overall on-road air quality was improved effectively, due to the 32.3% traffic flow reduction. The concentrations of PM₁₀, CO and NO₂ have reduced from 142.6 μg m⁻³, 3.02 mg m⁻³ and 118.7 μg m⁻³ to 102.0 μg m⁻³, 2.43 mg m⁻³ and 104.1 μg m⁻³. However, the different pollutants show diverse changes after the traffic control. PM₁₀ decreases most, and the reduction effect focusing on the first half-day even clears the morning peak, whereas CO and NO₂ have even reductions to minify the daily fluctuations on the whole. Opposite to the other pollutants, ozone shows an increase of concentration. The average reduction rate of PM₁₀, CO, NO₂ and O₃ are respectively 28%, 19.3%, 12.3% and −25.2%. Furthermore, the streets in east, west, south and north areas present different air quality improvements, probably induced by the varied background pollution in different regions around Beijing, along with the impact of wind force. This finding suggests the pollution control in the surrounding regions, not only in the urban area.     

Concentrations and elemental composition of particulate matter in the Buenos Aires underground system

Total suspended particulate (TSP) samples have been collected at six stations in the C and B lines of the Buenos Aires underground system and, almost simultaneously, at six ground level sites outside and nearby the corresponding underground stations, in the Oct 2005/Oct 2006 period. All these samples were analyzed for mass and elemental Fe, Cu, and Zn concentrations by using the Particle Induced X-ray Emission (PIXE) technique. Mostly, TSP concentrations were found to be between 152 μg m⁻³ (25% percentile) and 270 μg m⁻³ (75% percentile) in the platform of the stations, while those in outside ambient air oscillated from 55 μg m⁻³ (25% percentile) to 137 μg m⁻³ (75% percentile). Moreover, experimental results indicate that TSP levels are comparable to those measured for other underground systems worldwide. Statistical results demonstrate that subway TSP levels are about 3 times larger on average than those for urban ambient air. The TSP levels inside stations and outdoors are poorly correlated, indicating that TSP levels in the metro system are mainly influenced by internal sources.Regarding metal concentrations, the most enriched element in TSP samples was Fe, the levels of which ranged from 36 (25% percentile) to 86 μg m⁻³ (75% percentile) in Line C stations, while in Line B ones they varied between 8 μg m⁻³ (25% percentile) and 46 μg m⁻³ (75% percentile). As a comparison, Fe concentrations in ambient air oscillated between 0.7 μg m⁻³ (25% percentile) and 1.2 μg m⁻³ (75% percentile). Other enriched elements include Cu and Zn. With regard to their sources, Fe and Cu have been related to processes taking place inside the subway system, while Zn has been associated with outdoor vehicular traffic. Additionally, concerns about possible health implications based on comparisons to various indoor air quality limits and available toxicological information are discussed.     

Factors influencing silver recovery and power generation in bio-electrochemical reactors

The recovery of silver from Ag⁺ solution coupled with power generation was investigated in bio-electrochemical system (BES). In this system, chemical energy existing in the organic matter in the anode chamber can be converted biologically to electrical energy which can be used for the reduction of Ag⁺ ions in the cathode chamber. Results showed that type of substrate influenced the metabolic pathway and affected the cell voltage progression, and columbic efficiency. Silver recovery was not affected by increasing initial pH (2.0 to 7.0) and Ag⁺ concentration (100 to 1000 mg/L) in the catholyte, whereas power generation was improved. A maximum power density of 8258 mW/m³ and a columbic efficiency of 21.61% could be achieved with 1000 mg/L of Ag⁺. Ag⁺ ions were reduced to form metallic deposits as Ag⁰ crystals on the cathode surface, which were then confirmed by scanning electron microscope (SEM) image and energy dispersive X-ray (EDX) spectrum. The BES reactor had high silver removal (i.e., >96%) after 24 h of operation. When considering the crossover of Ag⁺ ions through the cation exchange membrane, the removal was in the range of 83.73–92.51%. This crossover was not considerable as compared to the Ag⁺ initial concentration. At higher initial Ag⁺ concentration (2000 mg/L), the silver removal decreased to 88.61% and the maximum power density decreased to 5396 mW/m³. This study clearly showed that BES can be employed for silver recovery, wastewater treatment, and also electricity generation.     

Particle size distribution of airborne Aspergillus fumigatus spores emitted from compost using membrane filtration

Information on the particle size distribution of bioaerosols emitted from open air composting operations is valuable in evaluating potential health impacts and is a requirement for improved dispersion simulation modelling. The membrane filter method was used to study the particle size distribution of Aspergillus fumigatus spores in air 50 m downwind of a green waste compost screening operation at a commercial facility. The highest concentrations (approximately 8 × 10⁴ CFU m⁻³) of culturable spores were found on filters with pore diameters in the range 1–2 μm which suggests that the majority of spores are emitted as single cells. The findings were compared to published data collected using an Andersen sampler. Results were significantly correlated (p < 0.01) indicating that the two methods are directly comparable across all particles sizes for Aspergillus spores.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

Microbial characterization of nitrification in a shallow, nitrogen-contaminated aquifer, Cape Cod, Massachusetts and detection of a novel cluster associated with nitrifying Betaproteobacteria

Groundwater nitrification is a poorly characterized process affecting the speciation and transport of nitrogen. Cores from two sites in a plume of contamination were examined using culture-based and molecular techniques targeting nitrification processes. The first site, located beneath a sewage effluent infiltration bed, received treated effluent containing O₂ (> 300 µM) and NH₄⁺ (51–800 µM). The second site was 2.5 km down-gradient near the leading edge of the ammonium zone within the contaminant plume and featured vertical gradients of O₂, NH₄⁺, and NO₃⁻ (0–300, 0–500, and 100–200 µM with depth, respectively). Ammonia- and nitrite-oxidizers enumerated by the culture-based MPN method were low in abundance at both sites (1.8 to 350 g^− 1 and 33 to 35,000 g^− 1, respectively). Potential nitrifying activity measured in core material in the laboratory was also very low, requiring several weeks for products to accumulate. Molecular analysis of aquifer DNA (nested PCR followed by cloning and 16S rDNA sequencing) detected primarily sequences associated with the Nitrosospira genus throughout the cores at the down-gradient site and a smaller proportion from the Nitrosomonas genus in the deeper anoxic, NH₄⁺ zone at the down-gradient site. Only a single Nitrosospira sequence was detected beneath the infiltration bed. Furthermore, the majority of Nitrosospira-associated sequences represent an unrecognized cluster. We conclude that an uncharacterized group associated with Nitrosospira dominate at the geochemically stable, down-gradient site, but found little evidence for Betaproteobacteria nitrifiers beneath the infiltration beds where geochemical conditions were more variable.     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

An assessment of indoor air quality in recent Mexican immigrant housing in Commerce City, Colorado

An indoor air quality assessment was conducted on 100 homes of recent Mexican immigrants in Commerce City, Colorado, an urban industrial community north of Denver. Head of households were administered a family health survey, filled out an activity diary, and participated in a home inspection. Carbon monoxide (CO) and carbon dioxide (CO₂) were measured for 24 h inside the main living area and outside of the homes. Harvard Impactors were used to collect 24-h samples of PM_2.5 at the same locations for gravimetric analysis. Dust samples were collected by vacuuming carpeting and flooring at four locations within the home and analyzed by ELISA for seven allergens. Mean indoor and outdoor PM_2.5 levels were 27.2 and 8.5 μg m⁻³, respectively. Indoor PM_2.5 and CO₂ were elevated in homes for which the number of hours with door/window open was zero compared to homes in which the number of hours was high (>15 h). Indoor PM_2.5 levels did not correlate with outdoor levels and tended to increase with number of inhabitants, and results indicate that the source of indoor particles were occupants and their activities, excluding smoking and cooking. Mean indoor CO₂ and CO levels were 1170 and 2.4 ppm, respectively. Carbon monoxide was higher than the 24-h National Ambient Air Quality Standard in 3 of the homes. The predominant allergens were cat (Fel d 1) and mouse (Mus m 1) allergens, found in 20 and 34 homes, respectively.     

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.     

An aerosol flow tube study of the interaction of N2O5 with calcite, Arizona dust and quartz

The interaction of N₂O₅ with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO₃) and quartz (SiO₂) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10⁻³ for CaCO₃, (8.6 ± 0.6) × 10⁻³ for Quartz and (9.8 ± 1.0) × 10⁻³ for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.     

Cation exchange in a glacial till drumlin at a road salt storage facility

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d^− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d^− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k_max = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d^− 1. The stable isotope-based biodegradation rate constant of 0.0027 d^− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d^− 1. With MM-kinetics a maximum degradation rate of k_max = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor ε_field of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.