Kinetics of the gas-phase reactions of alkylnaphthalenes with O3, N2O5 and OH radicals at 298 ± 2 K

Rate constants for the gas-phase reactions of the OH radical with 1-methylnaphthalene and of N₂O₅ with 1- and 2-methylnaphthalene and 2,3-dimethylnaphthalene have been determined at 298 ± 2 K by use of relative rate techniques. The rate constants determined were: for the reaction of OH radicals with 1-methylnaphthalene, (5.30 ± 0.48) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹; for the reaction of N₂O₅ with 1-methylnaphthalene, 2-methylnaphthalene and 2,3-dimethylnaphthalene, (3.3 ± 0.7) × 10⁻¹⁷, (4.2 ± 0.9) × 10⁻¹⁷ and (5.7 ± 1.9) × 10⁻¹⁷ cm³ molecule⁻¹ s⁻¹, respectively. In addition, an upper limit to the rate constant of 1.3 × 10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ was measured for the reaction of O₃ with 1-methylnaphthalene at 298 ± 2 K. These data, when combined with data from previous literature, allow the atmospheric gas-phase removal processes of these alkylnaphthalenes to be quantified.     

Organic acids in springtime wisconsin precipitation samples

A short-term study on organic acids in precipitation was conducted from 15 March to 1 June 1984 at two sites on the Wisconsin Acid Deposition Monitoring Network. Aliquots of collected samples were fixed with tetrachloromercurate (TCM) and analyzed for low molecular weight organic anions via ion-exclusion chromatography (ICE). Unfixed aliquots were subjected to standard network inorganic analyses. Of the 31 samples collected, 30 contained detectable concentrations of formate and acetate ions, with concentrations ranging from < 0.43 to 56μmol ℓ⁻¹ for the former and < 0.83 to 33 μmol ℓ⁻¹ for the latter. Propionate, oxalate and malonate ions were also detected in a number of samples. Statistical analysis of the combined organic and inorganic data set indicated that no significant differences existed between the concentrations of organic ions at the two sites; however, samples containing visible sediments had significantly greater concentrations than samples without sediments. Maximum contributions of the organic acids to precipitation-free acidity, calculated by assuming that the only sources of the measured formate and acetate were their respective acid forms, averaged 18.6% for samples with a pH ⩽ 5.0. Formate and acetate concentrations were highly correlated. Correlations between organic and inorganic ions were weak; NH⁺₄ and Ca²⁺ generally exhibited the highest, though still weak, correlations. The study emphasizes the need for further, longer-term investigations to determine the role of low molecular weight organic compounds in precipitation chemistry.     

Washout ratios of nitrate,non-sea-salt sulfate and sea-salt on Virginia key,Florida and on American Samoa

On Virginia Key, Miami, Florida, 257 rainwater samples were collected on a event basis from May 1982 to April 1985. At the same site, 171 aerosol samples were collected throughout 1984. All of these samples were analyzed for nitrate, non-sea-salt (NSS) sulfate and sodium to assess the temporal variations in the concentrations and to determine the washout ratios of each of the constituents. The annual volume-weighted mean concentrations in rainwater are: nitrate—0.51 μg ml⁻¹; NSS sulfate—0.74 μg ml⁻¹; Na—1.93 μg ml⁻¹. Only sodium exhibited a significant seasonal cycle; its concentrations were markedly higher during the winter. In aerosols, the mean concentrations are: nitrate—1.9 μg m⁻³; NSS sulfate—2.8 μg m³; Na—3.7 μg m⁻³. Nitrate and NSS sulfate exhibit consistent seasonal cycles with concentrations being significantly higher during the winter and spring. We estimate that wet deposition accounts for the majority of the total fluxes of each constituent: 80% for nitrate, 95 % for NSS sulfate, and 67% for Na. Annual washout ratios at Virginia Key arc similar for nitrate and NSS sulfate, 330 and 290, respectively. That for Na is about a factor of two higher, 550. Comparable long-term ratios were calculated for American Samoa based on aerosol data from the SEAREX program and rainwater data from the National Atmospheric Deposition Program: 270 for nitrate, 420 for NSS sulfate, and 520 for Na. The comparability of the Virginia Key and Samoa results suggest that these ratios may be applicable over a wide area of the world ocean. Estimates from nonconcurrent data for the washout ratios at Bermuda were factors of two to four higher. Regression equations for washout ratio vs event rainfall (logW = loga + blogR) at Virginia Key were essentially the same for all three constituents with ‘a’ ranging from 1100 to 1300 and ‘b’ ranging from −0.26 to −0.29. The coefficients for American Samoa were markedly different: ‘a’ ranged from 2900 to 3600 and ‘b’ ranged from −0.51 to −0.56.     

Seasonal variations in VOC emission rates from gorse (Ulex europaeus)

Seasonal variations of biogenic volatile organic compound (VOC) emission rates and standardised emission factors from gorse (Ulex europaeus) have been measured at two sites in the United Kingdom, from October 1994 to September 1995, within temperature and PAR conditions ranging from 3 to 34°C and 10–1300 μmol m⁻² s⁻¹, respectively. Isoprene was the dominant emitted compound with a relative composition fluctuating from 7% of the total VOC (winter) to 97% (late summer). The monoterpenes α-pinene, camphene, sabinene, β-pinene, myrcene, limonene, trans-ocimene and γ-terpinene were also emitted, with α-pinene being the dominant monoterpene during most the year. Trans-ocimene represented 33–66% of the total monoterpene during the hottest months from June to September. VOC emissions were found to be accurately predicted using existing algorithms. Standard (normalised) emission factors of VOCs from gorse were calculated using experimental parameters measured during the experiment and found to fluctuate with season, from 13.3±2.1 to 0.1±0.1 μg C (g dwt)⁻¹ h⁻¹ in August 1995 and January 1995, respectively, for isoprene, and from 2.5±0.2 to 0.4±0.2 μg C (g dwt)⁻¹ h⁻¹ in July and November 1995, respectively, for total monoterpenes. No simple clear relation was found to allow prediction of these seasonal variations with respect to temperature and light intensity. The effects of using inappropriate algorithms to derive VOC fluxes from gorse were assessed for isoprene and monoterpenes. Although on an annual basis the discrepancies are not significant, monthly estimation of isoprene were found to be overestimated by more than a factor of 50 during wintertime when the seasonality of emission factors is not considered.     

Rate constants for some oxidations of S(IV) by radicals in aqueous solutions

Rate constants were measured for several radical reactions important in the autoxidation of S(IV) in atmospheric droplets. For the reactions of the hydroxyl radical with sulfite and bisulfite, the rate constants were found to be 5.2 × 10¹⁰ and 4.5 × 10⁹ M⁻¹ s⁻¹, respectively. For the reaction of the dichloride radical anion with bisulfite, a rate constant of 3.4 × 10⁸M⁻¹s⁻¹ was obtained. The peroxysulfate radical was found to react with sulfite with a rate constant of 1.3 × 10⁷M⁻¹s⁻¹, but only an upper limit of 3×10⁵ could be derived for its reaction with bisulfite. In some cases, the rate constants are significantly different from those used previously in atmospheric models. The use of these results in a simple model suggests that secondary radical-radical reactions may be of considerable importance in the mechanism of sulfite autoxidation in the atmosphere.     

Oxidation of SO2 in rainwater and its role in acid rain chemistry

A limited survey of rainwater composition covering 80 precipitation events was carried out to establish the levels of soluble metal ions which may influence the oxidation rate of SO₂ in the aqueous phase. For 40 of the samples sodium sulphite was added at low concentrations and the rate of oxidation of S(IV) to S(VI) established. The first order rate constant k_s(IV) was found to vary over three orders of magnitude, from 10⁻⁵ to 10⁻² s⁻¹. pH and iron concentrations were found to be the most important factors affecting the rate. There was poor correlation between the rate of oxidation and the manganese, copper and zinc concentrations. The absolute values of the rate constants are lower than those used in recent modelling studies of atmospheric droplets and the importance of iron relative to manganese also differs from earlier studies.     

Photooxidation of methylhydroperoxide and ethylhydroperoxide in the aqueous phase under simulated cloud droplet conditions

The photooxidation of methylhydroperoxide (MHP) and ethylhydroperoxide (EHP) was studied in the aqueous phase under simulated cloud droplet conditions. The kinetics and the reaction products of direct photolysis and OH-oxidation were studied for both compounds. The photolysis frequencies obtained were J_MHP=4.5 (±1.0)×10⁻⁵ s⁻¹ and J_EHP=3.8 (±1.0)×10⁻⁵ s⁻¹ for MHP and EHP respectively at 6 °C. The rate constants of OH-oxidation of MHP at 6 °C were 6.3 (±2.6)×10⁸ M⁻¹ s⁻¹ and 5.8 (±1.9)×10⁸ M⁻¹ s⁻¹ relative to ethanol and 2-propanol respectively, and the rate constant of OH-oxidation of EHP was 2.1 (±0.6)×10⁹ M⁻¹ s⁻¹ relative to 2-propanol at 6 °C. The reaction products obtained were not only the corresponding aldehydes, but also the corresponding acids, and hydroxyhydroperoxides as primary reaction products. The yields for these products were sensitive to the pH value. The carbon balance was higher than 85% for all experiments, showing that most reaction products were detected. A chemical mechanism was proposed for each reaction, and the atmospheric implications were discussed.     

Scavenging of SO4− radical anions by mono- and dicarboxylic acids in the Mn(II)-catalyzed S(IV) oxidation in aqueous solution

The rate constants for reactions of the SO₄⁻ radical anion with some low molecular weight monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) and their anions using the laser flash photolysis-long path laser absorption (LFP-LPLA) technique were determined. The present study contains the first measured rate constants for SO₄⁻ reactions with glycolic, lactic, malic and malonic acid. The rate constants are found to be in the range from 10⁵ to 10⁷ M⁻¹ s⁻¹, with the lower values found for acids and higher values for their respective anions. In addition, the rate constants for scavenging of SO₄⁻ by all investigated organics in the Mn(II)-catalyzed S(IV) autoxidation at pH 4.5 and T=25 °C were determined by means of the reversed rate method. The comparison between these rate constants and the rate constants obtained by direct measurements confirms the proposed inhibiting mechanism for the Mn(II)-catalyzed S(IV) autoxidation in the presence of monocarboxylic acids. In the case of formic acid, which causes the highest inhibition, this mechanism can explain the second part of kinetic traces (i.e. after the induction period). Surprisingly, although dicarboxylic acids are reactive toward SO₄⁻ they do not contribute to the inhibition of S(IV) oxidation (especially malic and malonic acids).     

Atmospheric deposition of fluoride in the lower Tamar Valley,Tasmania

Soluble fluoride (F⁻), measured using an ion-selective electrode, was monitored during 1982–1983 in monthly bulk (wet and dry) atmospheric deposition samples collected at 17 locations in the lower Tamar Valley, Tasmania, where an aluminium (Al) smelter is located. Glass samplers (funnel-bottle type) were used, with duplications by plastic samplers at five locations later. The spatial and temporal variations in F⁻ deposition in relation to wind flow and rainfall are discussed, and its impact on the environment is highlighted. The mean deposition rates of F⁻, as measured from September 1982 to August 1983, ranged from about 90 μg m⁻² day⁻¹ at the intended ‘background’ location to 12,568 μg m⁻²day⁻¹ at a location about 1 km east-southeast from the smelter. The depositional fluxes of F⁻ and insoluble Al (another elemental tracer of the smelter) are significantly correlated (P < 0.001). They were much higher within 3 km of the smelter, where vegetation damage by fluoride contamination was most evident. However, air emissions from the smelter could travel at least 10 km up the valley. Wet deposition was the predominant removal process for F⁻ during autumn and winter, while dry deposition appeared to be more significant in summer. The plastic samplers collected about 8 and 17% more F⁻ and Al, respectively, but with higher standard deviations. Thus the variations observed could be largely due to sampling fluctuations.     

Winter-grazing reduces methane uptake by soils of a typical semi-arid steppe in Inner Mongolia,China

Steppe ecosystems are regarded as an important sink of atmospheric methane (CH₄) and grazing is hypothesized to reduce CH₄ uptake. However, firm experimental evidence is required to prove this hypothesis. Using a fully automated, chamber-based measuring system, we conducted continuous high-frequency (at a 3-h interval) measurements of CH₄ uptake in a Leymus chinensis steppe, which is a typical grassland ecosystem in Inner Mongolia, China. Two management regimes were investigated: ungrazed since 1999 (UG99) and winter-grazed since 2001 (WG01). Measurements were carried out continuously during the periods of June–September 2004, May–September 2005 and March–June 2006. During all of these periods, significantly lower mean CH₄ uptake (±S.E.) at WG01 (28±0.7 μg C m⁻² h⁻¹) as compared to UG99 (56±1.0 μg C m⁻² h⁻¹) (p<0.01) was found. Total CH₄ uptake during the growing seasons (May–September) 2004 and 2005 at WG01 and UG99 was quantified as 1.15 and 2.15 kg C ha⁻¹, respectively. Annual rates of CH₄ uptake were approximately 1.91 (WG01) and 3.58 kg C ha⁻¹ (UG99), respectively. These results indicate that winter-grazing of steppe significantly reduced atmospheric CH₄ uptake by ca. 47%. The winter-grazing practice may have inhibited CH₄ uptake by (a) increasing the likelihood of physiological water stress for CH₄-consuming bacteria during dry periods, (b) decreasing gas diffusion into the soil and, (c) reducing the populations of CH₄ oxidizing bacteria. These three mechanisms could have collectively or independently facilitated the observed inhibitory effects. Our results suggest that grazing exerts a considerable negative impact on CH₄ uptake in semi-arid steppes at regional scales. Notwithstanding, further studies involving year-round, intensive measurements of CH₄ uptake are needed.     

Atmospheric fate of acrylic acid and acrylonitrile: Rate constants with Cl atoms and OH radicals in the gas phase

Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with acrylic acid and acrylonitrile have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method with different reference compounds. Room temperature rate constants are found to be (in cm³ molecule⁻¹ s⁻¹): k₁(OH+CH₂CHC(O)OH)=(1.75±0.47)×10⁻¹¹, k₂(Cl+CH₂CHC(O)OH)=(3.99±0.84)×10⁻¹⁰, k₃(OH+CH₂CHCN)=(1.11±0.33)×10⁻¹¹ and k₄(Cl+CH₂CHCN)=(1.11±0.23)×10⁻¹⁰ with uncertainties representing ±2σ. This is the first kinetic study for these reactions under atmospheric pressure. The rate coefficients are compared with previous determinations taking into account the effect of pressure on the rate constants. The effect of substituent atoms or groups on the overall rate constants is analyzed in comparison with other unsaturated compounds in the literature. In addition, atmospheric lifetimes based on the homogeneous sinks of acrylic acid and acrylonitrile are estimated and compared with other tropospheric sinks for these compounds.     

PM10 measurements at McMurdo Station,Antarctica

PM₁₀ aerosols at McMurdo Station, Antarctica were sampled continuously during the austral summers of 1995–1996 and 1996–1997. PM₁₀ (particles with aerodynamic diameters less than 10 μm) mass concentrations at Hut Point, located less than 1 km from downtown McMurdo, averaged 3.4 μg m⁻³, more than an order of magnitude lower than the USEPA annual average National Ambient Air Quality Standard (NAAQS) of 50 μg m⁻³. Concentrations of methanesulfonate and nitrate were similar to those measured at other Antarctic coastal sites. Non-sea-salt sulfate (NSS) concentrations on Ross Island were higher than those found at other coastal locations. The average elemental carbon concentration (129 ng m⁻³) downwind of the station was two orders of magnitude higher than those measured at remote coastal and inland Antarctic sites during summer. Average sulfur dioxide concentrations (746 ng m⁻³) were 3–44 times higher than those reported for coastal Antarctica. Concentrations of Pb and Zn were 17 and 46 times higher than those reported for the South Pole. A methanesulfonate to biogenic sulfate ratio (R) of 0.47 was derived that is consistent with the proposed temperature dependence of R.     

Simultaneous absolute measurements of gaseous nitrogen species in urban ambient air by long pathlength infrared and ultraviolet-visible spectroscopy

Two new long pathlength spectrometers, utilizing 25-m basepath multiple reflection optical systems, were employed for the first time during an intercomparison of measurement methods for atmospheric nitrogenous species held at Claremont, CA, 11–19 September 1985. Measurement of nitrogenous species using these closed optical path systems, as opposed to single pass systems extending several kilometers, permit the resulting in situ absolute spectroscopic data to serve as benchmark values for point monitors employing denuders or filter packs. The FT-IR spectrometer was operated at a total pathlength of 1150 m and spectral resolution of 0.125 cm⁻¹, with corresponding detection sensitivities of 160 nmolem⁻³ for HNO₃ and 60 nmole m⁻³ for NH₃ (4 and 1.5 ppb, respectively). Concurrent measurements of HONO, NO₂ and NO₃ radicals were conducted with the differential optical absorption spectrometer operated at 800 m total pathlength with detection limits of 24, 160 and 0.8 nmole m⁻³ (0.6, 4 and 0.02 ppb) for HONO, NO₂, and NO₃ radicals, respectively.     

Formate,acetate and methanesulfonate measurements in antarctic ice: Some geochemical implications

Serious contamination problems are encountered when measuring organic acids in polar ice. Using an involved experimental protocol, methanesulfonate, formate and acetate have been investigated in ice core sections from Antarctica. With CH₃SO₃⁻ concentrations of a few ppb, HCOO⁻at a few tenths of ppb and CH₃COO⁻ around our detection limit, the organic acids represent only a small percentage of the total acidity in Antarctic ice.Analysis of the various possible sources indicates that methane is probably the major atmospheric precursor (via formaldehyde) of formate present in the ice.The significant presence of CH₃SO₃⁻ in Antarctic ice confirms the preponderant role played by marine biogenic emissions in the Antarctic sulfate budget. The CH₃SO₃⁻ ratio with respect to non-sea-salt sulfate is higher in Antarctic precipitation than in marine aerosol. Finally, CH₃SO₃⁻ in polar ice is suggested to be a more suitable parameter than excess sulfate for the study of marine biogenic emissions in the past.     

Chemical composition of snowfall in the high Arctic: 1990–1994

From 1990 to 1994 at Alert, Nunavut, Canada, weekly snow samples were collected under low wind conditions to avoid contamination by blowing snow. They were analysed for major ions, Br⁻, and the organic ions methylsulphonate, formate, acetate and propionate. In the Arctic, where annual precipitation is low and blowing snow is common, these observations are unique. On an equivalent weight basis, acids and sea salt in snowfall are mixed approximately equally from December to January but from March to May acids dominate. The acidity of snowfall increases progressively throughout the winter to a May peak of ∼16 μeq l⁻¹. SO₄²⁻, Br⁻, and the organic acids acetate, and propionate peak in snowfall after polar sunrise indicate the influence of enhanced photochemical reactions. The greater enrichment of halides relative to sea salt Na⁺ in snow compared to aerosols indicates that gaseous uptake by snowflakes is important in the removal of these substances from the atmosphere and their deposition on to the Earth's surface. There is a marked difference between the seasonal variation of enrichment of Cl⁻ and Br⁻ in snow. The latter show a marked increase after polar sunrise while the former does not. These results provide valuable baseline information on the ionic content of fresh snowfall to be used in understanding the results of snowpack chemistry and post-depositional process studies conducted in the high Arctic.     

Measurements of the aerosol concentrations of methanesulphonic acid,dimethyl sulphoxide and dimethyl sulphone in the marine atmosphere of the British Isles

Aerosol concentrations of methanesulphonic acid (MSA), dimethyl sulphoxide (DMSO) and dimethyl sulphone (DMSO₂) have been measured from landbased stations at Plymouth (Devon, U.K.), Galway (EIRE), and from various shipboard stations in the North Sea and the North Atlantic Ocean. MSA, DMSO and DMSO₂ all show seasonal cycles with spring/summer maxima and winter minima. The summer concentrations of MSA are approximately an order of magnitude higher than in winter. The general levels of MSA (July 1985 mean = 9.27 × 10⁻⁹ mol m⁻³, December 1986 mean = 1.14 × 10⁻⁹ mol m⁻³) are comparable to those reported from Cape Grim, Tasmania. Modelling indicates that neither MSA nor DMSO₂ are present in sufficient quantity to represent major oxidation pathways for dimethyl sulphide (DMS). Rate constant ratios for both the reactions of DMS and DMSO with OH and IO have been estimated. Hydroxyl radical does not appear to be reactive enough for it to be the major sink of atmospheric DMS. It is also shown that the rate constants for the destruction of DMSO (the main reaction product of the DMS/IO system) with either IO or OH are likely to be slow. Thus low tropospheric concentrations of DMSO tend to indicate that it also is not a major product of DMS oxidation.     

Aerosol scattering properties in northern China

The aerosol scattering properties were investigated at two continental sites in northern China in 2004. Aerosol light scattering coefficient (σ_sp) at 525 nm, PM₁₀, and aerosol mass scattering efficiencies (α) at Dunhuang had a mean value of 165.1±148.8 M m⁻¹, 157.6±270.0 μg m⁻³, and 2.30±3.41 m² g⁻¹, respectively, while these values at Dongsheng were, respectively, 180.2±151.9 M m⁻¹, 119.0±112.9 μg m⁻³, and 1.87±1.41 m² g⁻¹. There existed a seasonal variability of aerosol scattering properties. In spring, at Dunhuang PM₁₀, σ_sp, and α were 184.1±211.548 μg m⁻³, 126.3±89.6 M m⁻¹, and 1.05±0.97 m² g⁻¹, respectively, and these values at Dongsheng were 146.4±142.1 μg m⁻³, 183.4±81.7 M m⁻¹, and 1.98±1.52 m² g⁻¹, respectively. However, in winter at Dunhuang PM₁₀, σ_sp, and α were 158.1±261.4 μg m⁻³, 303.3±165.2 M m⁻¹, and 3.17±1.93 m² g⁻¹, respectively, and these values at Dongsheng were 155.7±170.1 μg m⁻³, 304.4±158.1 M m⁻¹, and 2.90±1.72 m² g⁻¹, respectively. σ_sp and α in winter were higher than that in spring at both the sites, which coincides with the characteristics of dust aerosol and pollution aerosol. Overall, the dominant aerosol types in spring and winter at both sites in northern China are dust aerosol and pollution aerosol, respectively.     

Atmospheric degradation of fluoroesters (FESs): Gas-phase reactivity study towards OH radicals at 298 K

Using the relative technique, rate coefficients have been measured for the gas phase reactions of hydroxyl radicals with four fluoroacetates, methyl trifluoroacetate (CF₃COOCH₃), ethyl trifluoroacetate (CF₃COOCH₂CH₃), methyl difluoroacetate (CF₂HCOOCH₃) and 2,2,2-trifluoroethyl trifluoroacetate (CF₃COOCH₂CF₃). Experiments were carried out at 296±2 K and atmospheric pressure (∼750 Torr) using nitrogen or synthetic air as bath gases. The following rate coefficients were derived for the reaction of OH radicals (in units of cm³ mol⁻¹ s⁻¹) with CF₃COOCH₃, k=(4.97±1.04)×10⁻¹⁴, CF₃COOCH₂CH₃, k=(2.64±0.59)×10⁻¹³, CF₂HCOOCH₃, k=(1.48±0.34)×10⁻¹³ and CF₃COOCH₂CF₃, (1.05±0.23)×10⁻¹³. The rate constants obtained are compared with previous literature data of other volatile organic compounds to establish reactivity trends. Atmospheric implications are discussed in terms of lifetimes and fates of the fluoroacetates in the troposphere.     

Measurements of JNO3− in snow by nitrate-based actinometry

Chemical actinometry was used to measure nitrate photolysis rate coefficients, J_NO3⁻, on and in snowpack at Summit, Greenland. Sealed glass tubes containing nitrate and a hydroxyl radical trapping system were buried in snow and exposed for between 2 and 24 h. Average J_NO3⁻ values for 2-h midday exposures in early June on surface snow were 10–14×10⁻⁷ s⁻¹. Averages over 24 h were 3.5–4.5×10⁻⁷ s⁻¹. These values reflect the integrated photon flux and also any variation of the nitrate photolysis rate with temperature. Attenuation of J_NO3⁻ within the firn was 0.03–0.04 cm⁻¹ for 24-h exposures and 0.08 cm⁻¹ for a 2-h exposure. Different attenuation coefficients may relate to differential light penetration due to changes in sun angle over the course of 24 h.     

Atmospheric deposition of macronutrients by pollen at a semi-remote site in northern Wisconsin

Pine pollen concentrations in air at a semi-remote site in northern Wisconsin attained levels of 18 and 25 μ m⁻³ in late May and early June of 1979 and 1981, respectively. The upper and lower limits for the deposition velocity of pine pollen at this site are approximately 30 and 1.3 cm s⁻¹, respectively. Consequently, the average annual pine pollen flux at this location for 1979 and 1981 was between 8.0 and 0.35 g m⁻². Deposition of total phosphorus and organic C by pollen dispersal are about 5–100% and 11–240%, respectively, of the measured bulk atmospheric loading rate in the region. Pine pollen fluxes of water-extractable K are about 10–230% of the average annual wet deposition, while the fluxes of waterextractable NO₃⁻ and SO₄⁻² by pollen appear to be negligible in comparison to the total atmospheric deposition (wet plus dry deposition) by other particles. The annual pine pollen flux to Crystal Lake, an oligotrophic seepage lake in the region, was estimated to be 6.5 g m⁻² during 1981. The deposition of total P by pollen to this lake was 5.8 kg a⁻¹, which is 45 % of the external input of total phosphorus. About 60% of the total P in samples of Pinus strobus and P. resinosa was dissolved reactive P, which is readily available for plant uptake. Because P is the limiting nutrient for many lacustrine systems and pine pollen dispersal coincides with the period of phytoplankton blooms in temperate-region lakes, this episodic input of P may represent an important source for seepage lakes whose external inputs are dominated by atmospheric deposition.