Aluminium speciation in surface waters from a Welsh upland area

The complete aluminium speciation of surface waters from an acidified catchment, during dry weather and during storm episodes, is obtained. For the first time, estimates of adsorbed aluminium (Al(ad)) are reported together with other aluminium species. Al(ad) is calculated from the difference between monomeric aluminium content before and after separation of suspended solids by filtration (0.015 microm pore diameter). This fraction was very significant (Al(ad) >; 40 microg litre(-1)) for samples with high suspended solids content (ss >; 20 mg litre(-1)) collected during storm episodes. Plots of pAl(3+) versus pH for samples collected during dry weather are approximated by a straight line, close to the solubility line of synthetic gibbsite, and have a slope of 2.5, which suggests that these samples were saturated with respect to gibbsite. The cloud of pAl(3+) versus pH points for samples from storm episodes has a near zero slope, and shows a significant degree of undersaturation with respect to synthetic gibbsite. Various mechanisms of aluminium mobilisation are discussed.     

Atmospheric deposition of polycyclic aromatic hydrocarbons near New England coastal waters

Wet and dry deposition of polycyclic aromatic hydrocarbons (PAHs) was measured at Nahant, Massachusetts, a peninsula jutting into Massachusetts Bay and Wolf Neck, a peninsula jutting into Casco Bay, Maine. Wet deposition (rain and snow) was collected in a funnel which drains into a shielded, temperature controlled receiving bottle. Dry deposition of gaseous and particulate PAHs was collected onto an exposed water surface. PAHs were analyzed by solid phase extraction and gas chromatography-mass spectrometry. Sixteen PAH species were analyzed, ranging from acenaphthylene to coronene. The mean wet deposition rate of the sum of the 16 species is 720 ng m⁻² cm⁻¹ precipitation at Nahant, and 831 ng m⁻² cm⁻¹ precipitation at Wolf Neck. Wet deposition is attributed to regional PAH emitting sources. Storm patterns appear to bring somewhat higher wet deposition of PAHs to Wolf Neck than to Nahant. The mean dry deposition rate is 95 ng m⁻² h⁻¹ at Nahant and 9.3 ng m⁻² h⁻¹ at Wolf Neck. The large difference is attributed to the fact that Nahant is close to the urban-industrial metropolitan Boston area and Logan International Airport, whereas Wolf Neck has no major PAH-emitting sources nearby. Individual measurements have an error bracket of ±30%. The Chemical Mass Balance model was used to apportion the dry deposition to source categories. At Nahant, nine samples gave valid statistical attributes with a mean apportionment: jet exhaust 35%, gasoline fueled vehicles 32%, diesel fueled vehicles 17%, wood combustion 13%, others 3%. At Wolf Neck, six samples yielded a mean apportionment: jet exhaust 30%, gasoline vehicles 28%, diesel vehicles 18%, wood combustion 16%, others 8%. There is a considerable variation between the samples. The apportionment is greatly dependent on the quality and selection of the model inputs, i.e. source signatures, which for PAHs are questionable.     

Volatile organic compounds in the surface waters of northern Greece

An investigation into the occurrence of volatile organic compounds (VOCs) was conducted for a period of two years in the surface waters of Northern Greece. Samples from four rivers and five lakes were taken seasonally and analyzed for VOCs. The analysis has been performed by purge-and-trap (PAT) gas chromatographic-mass spectrometric (GC-MS) technique. The most commonly encountered VOCs in surface waters were chloroform, carbon tetrachloride, trichloroethylene, dichlorobromomethane, tetrachloroethylene, and chlorodibromomethane.     

Polycyclic aromatic hydrocarbons in the bulk precipitation and surface waters of Northern Greece

Bulk (wet and dry) precipitation and surface water sampling was undertaken in the main plain of central Macedonia in Northern Greece. Fourteen polycyclic aromatic hydrocarbons (PAHs) included in the US EPA's priority pollutant list were analysed. The concentrations determined in bulk precipitation were in general within the range of values worldwide reported. Concentrations were highest in the cold months. Deposition fluxes of PAHs were of the same order of magnitude as reported data. The greatest values were found when high concentrations of PAHs in precipitation coincided with large precipitation amounts. The concentrations of PAHs in surface waters (main rivers, tributaries, ditches, etc) were in general lower than those in bulk precipitation, and among the lowest reported for European rivers, excepting Np and Ph. Bulk deposition and domestic effluents are suggested as being the main PAH sources into surface waters.     

Acid waters in upland Wales: causes, effects and remedies

Although situated on the western seaboard of the UK, and hence in the path of predominantly maritime air masses arriving directly from the Atlantic, Wales receives acidic deposition when winds are from the east. In conjunction with the highly base-poor rocks and soils found in the region, significant acidification of surface waters has occurred. Extensive afforestation in the Welsh uplands in the last 40 years has exacerbated acidification effects by elevating the loading of acidic anions received by catchments, thus increasing the concentrations of aluminium in watercourses. In considering possible remedial strategies, results of liming investigations from the Llyn Brianne Project in mid-Wales are presented. These studies have mainly involved liming small streams by a variety of catchment liming techniques. The most effective catchment treatments were those where finely ground CaCO3 was applied to the hydrological source areas at rates of up to 25 tonnes ha(-1). Possible drawbacks with such liming are discussed, although it is emphasized that liming is likely to be a component of any remedial strategy in the next 30 years until emissions reductions greater than those proposed in the forthcoming EC Directive are implemented.     

Long-term changes in elemental deposition at the earth's surface

The rate of deposition of elements at a point on the earth's surface can change, quite dramatically, even on relatively short time-scales, as a function of weather patterns. On a global scale volcanoes (and more rarely large meteors) can overwhelm steadier sources of trace elements. In recent centuries human activities have increased emissions to the atmosphere to a point where they are above those of natural sources for some of the rarer elements. On a longer time-scale climate change can also alter the deposition of elements, although such changes are often slower than those brought about through anthropogenic emissions. Changes in climate can also alter the distribution of deposition, but there are few studies estimating such changes. This paper uses estimates of the balance of natural and anthropogenic sources of a range of elements to examine the likely variation in deposition at the earth's surface. It particularly focuses on those elements regarded as toxic, whose concentrations seem likely to go on increasing in industrial areas.     

Seasonal variation in atmospheric aerosol concentration and composition at urban and rural sites in northern England

Seasonal variations in atmospheric aerosol concentration and composition have been determined at two nearby sites, one urban and one rural, near Leeds, W. Yorkshire. Aerosols, sampled on a daily basis and collected in the size ranges < 2.5 μm and 2.5−15 μm, were analysed for total mass, SO²⁻₄, NO⁻₃, Cl⁻ and NH⁺₄. Dark smoke and SO₂ were also measured at both sites. Results are given covering the period October 1982–September 1983. The average concentration of particles was higher at the urban site. The urban-rural difference in coarse particle concentration, which was about a factor of 2, was more significant than the difference in the fine particle concentration, which was only 1.3. Smoke and SO₂ concentrations showed strong wintertime maxima and summertime minima. Fine NO⁻₃ and Cl⁻ concentrations also had pronounced wintertime maxima and summertime minima attributed to the variation in volatility of their ammonium salts. Total mass, SO²⁻₄ and NH⁺₄ did not show any clear seasonal variations. Anti-cyclonic conditions in summer resulted in elevated mass concentrations of secondary pollutants, e.g. SO²⁻₄. The fine fraction contained ca 50% water-soluble inorganic ions at Leeds and slightly more at the rural site. These proportions showed little seasonal variation.     

Dry deposition of particles and canopy exchange: Comparison of wet,bulk and throughfall deposition at five forest sites in Italy

The contribution of dry deposition to the total atmospheric input of acidifying compounds and base cations is of overwhelming importance. Throughfall measurements provide an estimate of the total deposition to forest soils, including dry deposition, but some uncertainties, related to the canopy interaction processes, affect this approach. We compared the concentrations and the fluxes of the main ions determined in wet-only, bulk and throughfall samples collected at five forest sites in Italy. The contribution of coarse particles deposited onto the bulk samplers was of prime importance for base cations, representing on average from 16% to 46% of the bulk deposition. The extent of this dry deposition depended on some geographical features of the sites, such as the distance from the sea and the annual rainfall. The possibility of applying specific bulk/wet ratios to estimate the wet deposition proved to be limited by the temporal variability of these ratios, which must be considered together with the spatial variability. A direct comparison of the dry contribution deriving from the bulk–wet and the throughfall–wet demonstrated that an extensive natural surface (forest canopy) performs better than a small synthetic surface (funnel of the bulk sampler) in collecting dry deposition of SO₄²⁻, NO₃⁻ and Na⁺. The canopy exchange model was applied to both bulk and wet data to estimate the contribution of dry deposition to the total input of base cations, and the uncertainty associated to the model discussed. The exclusive use of bulk data led to a considerable underestimation of base cation dry deposition, which varies among the study sites.     

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.     

Wintertime wet and dry deposition in northern Michigan

Wet and dry deposition were monitored at the University of Michigan Biological Station in rural northern Michigan for three winters. Dry deposition was measured by both the conventional bucket method and by measuring increases in concentration in exposed, elevated snow samples. Average results of the two methods were in reasonable agreement. The cumulative wet and dry deposition quantities are in good agreement with snowpack accumulations until the first thaw period. Dry deposition to snow accounts for less than 15% of the total H⁺, SO²⁻₄, NO⁻₃ and NH⁺₄ and approximately 25% of the Ca ²⁺, Mg ²⁺, Na⁺, K⁺ and Cl⁻ during an average precipitation year. Snowpack measurements were also made under deciduous and red pine canopies. Decreases in H⁺ and NO⁻₃ were observed under the red pine canopy.     

Composition of wet and bulk deposition in Erzurum, Turkey

Seasonal variations in the chemical characteristics of wet and bulk deposition samples collected in Erzurum were investigated for the period March 2002-January 2003. Major cations (Ca2+, K+, Mg2+) and major anions (SO4(2-),NO3-) were determined in bulk and wet deposition samples; pH was also measured in wet deposition. The average pH of the wet deposition at Erzurum was 6.6 due to extensive neutralization of the acidity. A strong relationship between pH and SO4(2-) concentrations was observed in all seasons; however, only a weak relationship was found between pH and NO3-. On a seasonal basis, the correlation between Ca2+ and SO4(2-) concentrations was stronger in winter than in summer. Seasonal variations of ions were examined in both wet and bulk deposition samples. Although maximum concentrations of anions generally occurred during winter and spring, cation concentrations peaked in summer for both wet and bulk deposition. Results indicated that Ca2+ was the dominant cation and SO4(2-) the dominant anion in all deposition samples at Erzurum. Even though correlations among the crustal ions (calcium, magnesium and potassium) were high, the relationship between anthropogenic ions (sulfate and nitrate) was less clear in bulk deposition.     

Modelling acidification at Beacon Hill-a low rainfall, high pollutant deposition site in Central England

The model MAGIC (Model of Acidification of Groundwater In Catchments) has been applied to the Beacon Hill site, near Loughborough in Central England. This site is heavily impacted by wet and dry deposition of oxides of sulphur and nitrogen. The high acid inputs have caused soil acidification and acid stream waters. Long term simulations suggest that there has been a major decline in alkalinity and pH over the past 50 years. Despite recent reductions in deposition levels, soils and streams are predicted to continue to acidify in the future. For this heavily impacted site, deposition must be reduced by 80-90% to reverse the acidification trend and allow recovery of soil and stream waters.     

Practical considerations for addressing uncertainties in monitoring bulk deposition

The assessment of the deposition of both wet (rain and cloud) and dry sedimenting particles is a prerequisite for estimating element fluxes in ecosystem research. Many nations and institutions operate deposition networks using different types of sampler. However, these samplers have rarely been characterized with respect to their sink properties. Major errors in assessing bulk deposition can result from poor sampling properties and defective sampling strategies. Relevant properties are: sampler geometry and material, in particular the shape of the rim; sink properties for gases and aerosols; and microbial transformations of the collected samples. An adequate number of replicates allows the identification of samples which are contaminated, in particular by bird droppings. The paper discusses physical and chemical properties of the samplers themselves. The dependence of measurement accuracy on the number of replicates and the sampling area exposed is discussed. Recommendations are given for sampling strategies, and for making corrections and substitution of missing data.     

Error estimations of dry deposition velocities of air pollutants using bulk sea surface temperature under common assumptions

It is well known that skin sea surface temperature (SSST) is different from bulk sea surface temperature (BSST) by a few tenths of a degree Celsius. However, the extent of the error associated with dry deposition (or uptake) estimation by using BSST is not well known. This study tries to conduct such an evaluation using the on-board observation data over the South China Sea in the summers of 2004 and 2006. It was found that when a warm layer occurred, the deposition velocities using BSST were underestimated within the range of 0.8–4.3%, and the absorbed sea surface heat flux was overestimated by 21 W m^?2. In contrast, under cool skin only conditions, the deposition velocities using BSST were overestimated within the range of 0.5–2.0%, varying with pollutants and the absorbed sea surface heat flux was underestimated also by 21 W m^?2. Scale analysis shows that for a slightly soluble gas (e.g., NO₂, NO and CO), the error in the solubility estimation using BSST is the major source of the error in dry deposition estimation. For a highly soluble gas (e.g., SO₂), the error in the estimation of turbulent heat fluxes and, consequently, aerodynamic resistance and gas-phase film resistance using BSST is the major source of the total error. In contrast, for a medium soluble gas (e.g., O₃ and CO₂) both the errors from the estimations of the solubility and aerodynamic resistance are important. In addition, deposition estimations using various assumptions are discussed. The largest uncertainty is from the parameterizations for chemical enhancement factors. Other important areas of uncertainty include: (1) various parameterizations for gas-transfer velocity; (2) neutral-atmosphere assumption; (3) using BSST as SST, and (4) constant pH value assumption.     

Elevated atmospheric deposition and dynamics of mercury in a remote upland forest of southwestern China

Mt. Gongga area in southwest China was impacted by Hg emissions from industrial activities and coal combustion, and annual means of atmospheric TGM and PHg concentrations at a regional background station were 3.98 ng m⁻³ and 30.7 pg m⁻³, respectively. This work presents a mass balance study of Hg in an upland forest in this area. Atmospheric deposition was highly elevated in the study area, with the annual mean THg deposition flux of 92.5 μg m⁻² yr⁻¹. Total deposition was dominated by dry deposition (71.8%), and wet deposition accounted for the remaining 28.2%. Forest was a large pool of atmospheric Hg, and nearly 76% of the atmospheric input was stored in forest soil. Volatilization and stream outflow were identified as the two major pathways for THg losses from the forest, which yielded mean output fluxes of 14.0 and 8.6 μg m⁻² yr⁻¹, respectively.     

Physicochemical forms of technetium in surface water covering paddy and upland fields

The behavior of an element in the environment depends on its physicochemical form. Basic data for the behavior of technetium in an agricultural environment were obtained by determining the physicochemical forms of Tc in 28 surface water samples from paddy and upland fields. Most of the (95m)Tc was present as TcO(4)(-) in the samples. The relative amount of this chemical form was 72% on average. A significant amount of insoluble Tc (particles more than 0.2 microm in size), however, was found in some samples. The maximum amount of the insoluble Tc was 91%. Other forms were found in insignificant amounts. The amount of insoluble Tc was relatively high in paddy soil samples. Paddy soils, gley soils and gray lowland soils were particularly effective in the insolubilization of Tc. Among the soil characteristics studied, cation exchange capacity, anion exchange capacity, and active aluminum showed significant correlations with the relative amount of insoluble Tc. When microorganisms were eliminated from the surface water samples before the addition of (95m)TcO(4)(-), little insoluble Tc was found, suggesting that microorganisms cause the physicochemical transformation. These results showed that the physicochemical form of Tc changes from TcO(4)(-) to insoluble forms in surface water covering paddy fields. The insoluble forms would restrict the mobility of Tc in paddy fields.     

Phosphorus-based metabolic pathway tracers in surface waters

Environmental Science and Pollution Research - Trophic status in surface waters has been mostly monitored by measuring soluble reactive phosphorus (SRP) and total phosphorus (TP). Additional to...     

Seasonal and air mass trajectory effects on dissolved organic matter of bulk deposition at a coastal town in south-western Europe

Rainwater contains a complex mixture of organic compounds which may influence climate, terrestrial and maritime ecosystems and thus human health. In this work, the characteristics of DOM of bulk deposition at a coastal town on the southwest of Europe were assessed by UV–visible and three-dimensional excitation–emission matrix fluorescence spectroscopies and by dissolved organic carbon (DOC) content. The seasonal and air mass trajectory effects on dissolved organic matter (DOM) of bulk deposition were evaluated. The absorbance at 250 nm (UV_250nm) and integrated fluorescence showed to be positively correlated with each other, and they were also positively correlated to the DOC in bulk deposition, which suggest that a constant fraction of DOM is likely to fluoresce. There was more chromophoric dissolved organic matter (CDOM) present in summer and autumn seasons than in winter and spring. Bulk deposition associated with terrestrial air masses contained a higher CDOM content than bulk deposition related to marine air masses, thus highlighting the contribution of terrestrial/anthropogenic sources.