Vertical profiles of air pollutants in a spruce forest — analysis of adherent water,throughfall and deposits on surrogate surfaces

Vertical profiles of air pollutants were studied in a spruce forest, which is damaged mainly in the upper parts of the canopy. The sampling included plant surface water, throughfall and surrogate surfaces at five different heights. For most components a low amount of precipitation after a dry period yielded in vertical profiles of the plant surface water shaped by the wind speed. If there was enough precipitation to start wash-off, the maximum of the concentrations shifted downwards. An exception was the acidity, which increased continuously from the top to the bottom of the trees. The deposition on vertically orientated surfaces and face up orientated surfaces were in the same order of magnitude, but the deposition on face down orientated surfaces was negligible.     

Influence of usage and chemical–physical properties on the atmospheric transport and deposition of pesticides to agricultural regions of Manitoba,Canada

This study quantified the masses of 14 pesticides deposited as wet (precipitation) versus dry (gaseous and particle) atmospheric deposition at a research farm in southwestern Manitoba, Canada. The concentration in air of these pesticides was also measured. Total bulk deposition amounts (wet + dry) ranged from 0.009 to 2.3 μg m^?2 for the 12 pesticides detected, and for the six pesticides with both wet and dry deposition detections, dry deposition contributed 12–51% of the total deposition over the crop growing season. Although not applied at the site, eight herbicides registered for use in Canada, as well as lindane (γ-HCH), were all frequently detected (92–100%) in the 12 air samples analyzed during the crop growing season, with by-product isomer α-HCH (75%), clopyralid (50%) and atrazine (8%) detected to a lesser extent. The chemical’s physicochemical properties and the relative mean mass of each agricultural pesticide applied in the province of Manitoba and in a 13 km radius were significant parameters in explaining the trends in the concentrations of pesticides detected in our samples. The important contribution of dry deposition to total pesticide deposition warrants greater attention in arid and semi-arid areas such as the Prairie Region of Canada, also because under a changing climate this region is estimated to experience more severe droughts while the more favorable conditions predicted for pest infestations could lead to increased pesticide applications in agricultural and urban areas.     

Dry deposition of 4–50 μm dolomite particles on vegetation,flat surfaces and deposition gauges

Dry deposition of dolomite particles from a small plume onto various kinds of surfaces was studied. The concentration was measured in the air via isokinetic sampling on filters. The deposition and size distribution of the deposited particles were determined with a sedimentation scale. The results show significant variations in size distribution of deposited material and deposition velocity with wind velocity, particle size and type of surface. Clear indications of resuspension and ‘bounce-off’ were found.     

Zn isotope study of atmospheric emissions and dry depositions within a 5 km radius of a Pb–Zn refinery

The present paper examines the use of zinc isotopes as tracers of atmospheric sources and focuses on the potential fractionation of Zn isotopes through anthropogenic processes. In order to do so, Zn isotopic ratios are measured in enriched ores and airborne particles associated with pyrometallurgical activities of one of the major Pb–Zn refineries in France. Supporting the isotopic investigation, this paper also compares morphological and chemical characteristics of Zn particles collected on dry deposition plates (“environmental samples”) placed within a 5 km radius of the smelter, with those of Zn particles collected inside the plant (“process samples”), i.e. dust collected from the main exhaust system of the plant. To ensure a constant isotopic “supply”, the refinery processed a specific set of ores during the sampling campaigns, as agreed with the executive staff of the plant. Enriched ores and dust produced by the successive Zn extraction steps show strong isotope fractionation (from ?0.66 to +0.22‰) mainly related to evaporation processes within the blast furnaces. Dust from the main chimney displays a δ⁶⁶Zn value of ?0.67‰. Application of the Rayleigh equation to evaluate the fractionation factor associated with the Zn vapor produced after a free evaporation gives a range of α_ore/vapor from 1.0004 to 1.0008. The dry deposits, collected on plates downwind of the refinery, display δ⁶⁶Zn variations of up to +0.7‰. However, it is to be noted that between 190 and 1250 m from the main chimney of the refinery, the dry deposits show a high level of large (>10 μm) Zn, S, Fe and O bearing aggregates characterized by positive δ⁶⁶Zn values (+0.02 to +0.19‰). These airborne particles probably derive from the re-suspension of slag heaps and local emissions from the working-units. In contrast, from 1720 to 4560 m, the dry deposits are comprised of small (PM10) particles, including spherical Zn-bearing aggregates, showing negative δ⁶⁶Zn values (?0.52 to ?0.02‰). Our results suggest that the source of the distal dry fallouts is the main chimney plume, whose light Zn isotopic signature they preserve. Based on Zn isotopic analysis in combination with morphological and chemical characteristics of airborne particles, the present study suggests the traceability of smelter dusts by Zn isotopes.     

An assessment of source contributions to the ozone concentrations in southern Ontario, 1979–1985

Source contributions to the surface O₃ concentrations in southern Ontario were assessed for the 1979–1985 period. Ozone episode analyses indicate a frequency of about nine episodes per year (15 episode-days). These occur primarily in the summer months and are generally manifestations of the northern extent of the O₃ problem in eastern North America. Widespread elevated O₃ levels tend to occur under weather classes indicative of back or centre of the high pressure situations and associated flow/trajectory from areas south/southwest of the lower Great Lakes. These episodes vary considerably from year-to-year. Local impacts on O₃ levels are generally small.A study of O₃ levels during cloud-free summer days for the period 1981–1985 gave local ‘background’ O₃ levels of about 20–30 ppb daily and 30–50 ppb hourly maxima. The O₃ contributions from the U.S. to southern Canada (assuming local ‘background’ O₃ levels to be independent of wind direction) were estimated to be 30–35 ppb daily and 30–50 ppb hourly maxima. These results indicate an overall O₃ contribution of about 50–60% from the U.S. to southern Ontario. For episode-days, the U.S. contribution is even more significant.     

Distribution,persistence, and fate of mexacarbate in the aquatic environment of a mixed‐wood boreal forest

Abstract

The distribution and persistence of aerially applied mexacarbate were studied in a New Brunswick aquatic forest environment after spraying twice at a dosage of 70 g A.l./ha using a fixed‐wing aircraft. Average droplet density (drops/cm²) and ground deposition (g A.1./ha) between the two applications differed considerably. The values for the first and second applications were 1.7 and 0.73, and 5.2 and 2.0, respectively; but the average NMD (20 μm) and VMD (36 μm) for both applications were nearly the same. The maximum 1‐h postspray concentrations of mexacarbate in the stream and pond waters were 0.73 and 18.74 ppb, respectively. Concentrations fell rapidly to below detection limits within 12 h in stream and within 3 d in pond water. Cattails (Typha latifolia), manna grass (Glyceria borealis) and bog moss (Sphagnum sp.) collected from the pond contained peak 1‐h postspray concentrations of 720, 482 and 81 ppb, respectively. The concentration levels decreased rapidly and the average half‐lives of the chemical in them were about 3.9, 8.5 and 2.0 h. Bog moss, stream moss (Fontinalis sp.), watercress (Nasturtium officinalis), buttercup (Ranunculus aquatilis) and green alga (Drapamaldia sp.) sampled from the stream sites did not contain measurable levels of mexacarbate. Also, caged and wild tadpoles (Rana clamitans melanota) from the pond, and brook trout (Salvelinus fontinalis) (caged and wild), Atlantic salmon (Salmo salar) (wild) and mayfly nymphs (Ephemeralla sp.) collected from the stream did not contain any of the material. Mexacarbate was not detected in stream and pond sediments. The demethylated products, 4‐methylamino and 4‐amino‐3,5‐xylyl methylcarbamates and the phenol, 4‐dimethylamino‐3,5‐xylenol, were frequently detected as metabolites in water and in the aquatic plants. The presence of these compounds showed that demethylation and hydrolytic routes are the major metabolic pathways for the dissipation of mexacarbate from these substrates.     

Atmospheric concentrations,gaseous–particulate distribution,and carcinogenic potential of polycyclic aromatic hydrocarbons in Assiut,Egypt

The concentrations of 15 priority PAHs were determined in the atmospheric gaseous and particulate phases from nine sites across Assiut City, Egypt. While naphthalene, acenaphthene, and fluorene were the most abundant in the gaseous phase with average concentrations of 377, 184, and 181 ng/m³, benzo[b]fluoranthene, chrysene, and benzo[g,h,i]perylene showed the highest levels in the particulate phase with average concentrations of 76, 6, and 52 ng/m³. The average total atmospheric concentration of target PAHs (1,590 ng/m³) indicates that Assiut is one of the highest PAH-contaminated areas in the world. Statistical analysis revealed a significant difference between the levels of PAHs in the atmosphere of urban and suburban sites (P?=?0.029 and 0.043 for gaseous and particulate phases, respectively). Investigation of diagnostic PAH concentration ratios revealed vehicular combustion and traffic exhaust emissions as the major sources of PAHs with a higher contribution of gasoline rather than diesel vehicles in the sampled areas. Benzo[a]pyrene has the highest contribution (average?=?32, 4 % for gaseous and particulate phases) to the total carcinogenic activity (TCA) of atmospheric PAHs. While particulate phase PAHs have higher contribution to the TCA, gaseous phase PAHs present at higher concentrations in the atmosphere are more capable of undergoing atmospheric reactions to form more toxic derivatives.     

A combined model–observation approach to estimate historic gridded fields of PM2.5 mass and species concentrations

This paper introduces a methodology for estimating gridded fields of total and speciated fine particulate matter (PM_2.5) concentrations for time periods and regions not covered by observational data. The methodology is based on performing long-term regional scale meteorological and air quality simulations and then integrating these simulations with available observational data. To illustrate this methodology, we present an application in which year-round simulations with a meteorological model (the National Center for Atmospheric Research/Penn State Mesoscale Model, hereafter referred to as MM5) and a photochemical air quality model (the Community Multiscale Air Quality Model, hereafter referred to as CMAQ) have been performed over the northeastern United States for 1988–2005. Model evaluation results for total PM_2.5 mass and individual species for the time period from 2000 to 2005 show that model performance varies by species, season, and location. Therefore, an approach is developed to adjust CMAQ output with factors based on these three variables. The adjusted model values for total PM_2.5 mass for 2000–2005 are compared against independent measurements not utilized for the adjustment approach. This comparison reveals that the adjusted model values have a lower root mean square error (RMSE) and higher correlation coefficients than the original model values. Furthermore, the PM_2.5 estimates from these adjusted model values are compared against an alternate method for estimating historic PM_2.5 values that is based on PM_2.5/PM₁₀ ratios calculated at co-located monitors. Results reveal that both methods yield estimates of historic PM_2.5 mass that are broadly consistent; however, the adjusted CMAQ values provide greater spatial coverage and information for PM_2.5 species in addition to total PM_2.5 mass. Finally, strengths and limitations of the proposed approach are discussed in the context of potential uses of this method.     

Wet deposition of mercury in the U.S. and Canada, 1996–2005: Results and analysis of the NADP mercury deposition network (MDN)

One of the most critical measurements needed to understand the biogeochemical cycle of mercury, and to verify atmospheric models, is the rate of mercury wet-deposition. The Mercury Deposition Network (MDN) operates sites across North America to monitor total mercury in wet-deposition. MDN's primary goal is to provide both spatial and temporal continental-scale observations of mercury wet-deposition fluxes to support researchers, modelers, policy-makers and the public interest. MDN represents the only continental-scale mercury deposition database with a >10-year record of continuous values. This study provides analysis and interpretation of MDN observations at 10 years (1996–2005) with an emphasis on investigating whether rigorous, statistically-significant temporal trends and spatial patterns were present and where they occurred. Wet deposition of mercury ranges from more than 25 μg m^?2 yr in south Florida to less than 3 μg m^?2 yr in northern California. Volume-weighted total mercury concentrations are statistically different between defined regions overall (Southeast ≈ Midwest > Ohio River > Northeast), with the highest in Florida, Minnesota, and several Southwest locations (10–16 ng L^?1). Total mercury wet-deposition is significantly different between defined regions (Southeast > Ohio River > Midwest > Northeast). Mercury deposition is strongly seasonal in eastern North America. The average mercury concentration is about two times higher in summer than in winter, and the average deposition is approximately more than three times greater in summer than in winter. Forty-eight sites with validated datasets of five years or more were tested for trends using the non-parametric seasonal Kendall trend test. Significant decreasing mercury wet-deposition concentration trends were found at about half of the sites, particularly across Pennsylvania and extending up through the Northeast.     

To what extent are hepatic concentrations of heavy metals in Anguilla anguilla at a site in a contaminated estuary related to body size and age and reflected in the metallothionein concentrations?

We explored how hepatic [metal]s in Anguilla anguilla at a contaminated estuarine site are influenced by body size, age and season, and the extent that [Cu], [Cd] and [Zn]s are reflected in [metallothionein (MT)]s. Although each [metal] and [MT] increased significantly with length, weight and age, those biotic variables explained <10% of the variation in each [metal] and only 11-16% for [MT]. Seasonal changes in [Cu] and [Cd] were paralleled by [MT]. The variation in [MT] explained by Cu (42%) was greater than by Zn (16%) and Cd (13%), and seasonally lay between 43 and 69% for those metals collectively. Thus, hepatic [MT] in eels is closely correlated with hepatic [heavy metal]s. However, the great variability among [MT]s for eels of similar sizes and ages, which reflects marked variability in hepatic [heavy metal]s, means that this variable reflects imprecisely the contamination level at a particular site.     

Determination of Atmospheric Nitrogen Input to Lake Greenwood,South Carolina: Part 2—Gaseous Measurements and Modeling

Abstract

The Reedy River branch of Lake Greenwood, SC, has repeatedly experienced summertime algal blooms, upsetting the natural system. A series of experiments were carried out to investigate atmospheric nitrogen (N) input into the lake. N was examined because of the insignificant phosphorus dry atmospheric flux and the unique nutrient demands of the dominant algae (Pithophora oedogonia) contributing to the blooms. Episodic atmospheric measurements during January and March 2001 have shown that the dry N flux onto the lake ranged from 0.9 to 17.4 kg N/ha-yr, and on average is caused by nitric acid (HNO₃; 31%), followed by nitrogen dioxide (NO₂; 23%), fine ammonium (NH₄ ⁺; 20%), coarse nitrate (NO₃ ^?; 16%), fine NO₃ ⁺ (5%), and coarse NH₄ ⁺ (5%). Similar measurements in Greenville, SC (the upper watershed of the Reedy River), showed that the dry N deposition flux there ranged from 1.4 to 9.7 kg N/ha-yr and was mostly caused by gaseous deposition (40% NO₂ and 40% HNO₃). The magnitude of this dry N deposition flux is comparable to wet N flux as well as other point sources in the area. Thermodynamic modeling showed low concentrations of ammonia, relative to the particulate NH₄ ⁺ concentrations.     

Study on ambient concentrations of PM10, PM10–2.5, PM2.5 and gaseous pollutants. Trace elements and chemical speciation of atmospheric particulates

This study provides the first comprehensive report on mass concentrations of particulate matter of various sizes, inorganic and organic gas concentrations monitored at three sampling sites in the city of Palermo (Sicily, Italy). It also provides information on the water-soluble species and trace elements. A total of 2054 PM₁₀ (1333) and PM_2.5 (721) daily measurements were collected from November 2006 to February 2008. The highest mass concentrations were observed at the urban stations, average values being about two times higher than those at the suburban (control) site. Time variations in PM₁₀ and also PM_10–2.5 were observed at the urban stations, the highest concentrations being measured in autumn and winter. CO, NOx, NO₂, benzene, toluene and o-xylene concentrations peaked in autumn and winter, a pattern similar to those recorded for PM₁₀ and PM_10–2.5 mass levels, indicating the importance of traffic emissions in urban air pollution. 91% and 51% of the benzene measurements exceeded the limit of 5 μg m^?3 at the two urban monitoring sites. Trace elements (As, Ba, Cr, Cu, Mo, Pb, Sb) suspected of being introduced into the atmosphere mainly by anthropogenic activities, were highly enriched with respect to local soil. Results indicate that a large fraction of PM₁₀ (31–47% in weight) and PM_2.5 (29% in weight) is made up of water-soluble ions. Ammonium sulphate and nitrate particles accounted for 14–29 wt% of particulate matter mass concentrations. Crustal and marine components, combined, account for 41% and 49% in PM_2.5 and PM₁₀, respectively. The calculated deficits in Cl^- and NH₄⁺ ions suggest that a proportion of these ions are lost, via the formation of gaseous NH₄Cl or HCl and NH₃.     

Fate of nickel in a lime-stabilized biosolid,a calcareous soil and soil–biosolid mixtures

Soil contamination with anthropogenic metals resulting from biosolid application is widespread around the world. To better predict the environmental fate and mobility of contaminants, it is critical to study the capacity of biosolid-amended soils to retain and release metals. In this paper, nickel adsorption onto a calcareous soil, a lime-stabilized biosolid, and soil–biosolid mixtures (30, 75, and 150 t biosolid/ha) was studied in batch experiments. Sorption experiments showed that (1) Ni adsorption was higher onto the biosolid than the calcareous soil, and (2) biosolid acted as an adsorbent in the biosolid–soil mixtures by increasing Ni retention capacity. The sorption tests were complemented with the estimation of Ni adsorption reversibility by successive applications of extraction solutions with water, calcium (100 mg/L), and oxalic acid (equivalent to 100 mg carbon/L). It has been shown that Ni desorption rates in soil and biosolid-amended soils were lower than 30 % whatever the chemical reagent, indicating that Ni was strongly adsorbed on the different systems. This adsorption/desorption hysteresis effect was particularly significant at the highest biosolid concentration (150 t/ha). Finally, an adsorption empirical model was used to estimate the maximum permissible biosolid application rate using French national guideline. It has been shown that desorption effects should be quantitatively considered to estimate relevant biosolid loadings.     

Modelling atmospheric bulk deposition of Pb,Zn and Cd near a former Pb–Zn mine in West Greenland using transplanted Flavocetraria nivalis lichens

Atmospheric deposition of lead (Pb), zinc (Zn) and cadmium (Cd) was investigated near the former Black Angel Pb–Zn mine in Maarmorilik, West Greenland during 2010–2011. Thalli of the lichen Flavocetraria nivalis were transplanted from an uncontaminated site into sites near the mine and collected the following year. At 20 of the total 21 sites, concentrations of Pb, Zn and Cd were significantly elevated in lichens after 1 year of transplantation compared to initial concentrations. Elevated concentrations were observed within a distance of approx. 20 km from the mining area. Concentrations decreased with increasing distance from the mine and the relation was well described using a power function with a negative exponent (r² = 0.90; 0.83 and 0.83 for Pb; Zn and Cd). To examine the relation between metal concentrations/uptake in lichen transplants and atmospheric bulk deposition, 10 Bergerhoff dust samplers were placed near lichen transplants and samplers and lichens were collected after a 7-weeks exposure period. A significant linear correlation was observed between metal concentrations in lichen transplants and atmospheric bulk metal deposition (r² = 0.94; 0.88 and 0.89 for Pb; Zn and Cd). Combining the results and including an area distribution within a defined metal deposition area, the “annual” deposition of Pb, Zn and Cd as dust was estimated during the 2010–2011 snow-free period (～5 months). The results reveal that 20 years after mine closure, 770 kg Pb, 3700 kg Zn and 24 kg Cd were still being deposited as dust per year (snow-free period only) within a distance of 20 km from the mine.     

Increased nitrogen in runoff and soil following 13 years of experimentally increased nitrogen deposition to a coniferous-forested catchment at Gårdsjön, Sweden

Beginning in 1991, we have added nitrogen (N) to the 0.5-ha, N-poor, coniferous-forested catchment G2 NITREX at G?rdsj?n, Sweden, to investigate the consequences of chronic elevated N deposition. We have added 40 kg N ha-1 yr-1 in fortnightly doses of NH4NO3 to the ambient 15 kg N ha-1 yr-1 by means of a sprinkling system. NO3 concentrations in runoff increased during 13 years from<1 to 70 microeq L-1, and in 2004 comprised about 10% of N input. Inhibition of NO3 immobilisation due to increased availability of NH4 might explain the increased leaching of NO3. C and N pools in the forest floor increased but C/N ratio has not changed. The increase in NO3 leaching thus occurred independently of change in C/N ratio. The results from G?rdsj?n demonstrate that increased leaching of inorganic N and decrease in C/N ratio respond to increased N deposition at greatly different time scales.