Evaluation of Air Quality over the Black Sea: Major Ionic Composition of Rainwater

This article attempts to put the light on the air quality of the Black Sea region of Turkey. In addition to that, it endeavors to locate the possible sources of the different pollutants at local, regional and long range transported scales. About 196 rainwater samples were collected over the Black Sea region of Amasra between 1995 and 1999, and analyzed for major ions and trace elements using spectrophotometric techniques. Andersen wet only rain samples were used to collect rain events, where the rain sample was filtered inline using 0.45 m cellulose acetate filters. Major anions (SO₄ ^2-, NO₃ ^- and Cl^-) were determined using ion chromatography, whereas metals (Ca, Mg, Al, Fe, Na, K), werequantified using ICP-AES. This study shows that, the Black Sea region receives different amounts and types of anthropogenic pollutants via long-range transport according to trajectory models. Although the pH of rain water is not considered acidic (pH = 5.21) yet the neutralizing species are lower than other sites around Europe.     

Study of Bulk and Sub-Event Wet Deposition in Gebze,Turkey

This study presents the chemical composition of bulk deposition during the period of February 1996–May 1997 and the chemical composition of sub-event wet deposition on 13 August 1997 in Gebze. Samples were analyzed for SO₄ ^2-, NO₃ ^-, Cl^-,Ca²⁺, Mg²⁺, K⁺, Na⁺, and NH₄ ⁺ in addition to pH. The source of some ionic components in the bulk deposition such as K⁺ and Ca²⁺ were found to be the terrestrial regions, as expected. The (non-sea Cl^-)/Cl^- ratio of 0.05 suggests that the very large portion of Cl^- in the bulkdeposition was of marine origin. The ratio of (non-sea SO₄ ^2-)/SO₄ ^2- varied between 0.86 and 0.99,indicating that the main source of sulfate was not the sea. It is found that the sulfate and calcium concentrations were highest in summer and lowest in fall. The analysis of bulk deposition also indicated that nearly 24% of the events were acidic (pH < 5.6). During sub-event wet deposition collectedon the same site pH decreased continually, and during the passageof cold front concentrations of Cl^-, SO₄ ^2- and NO₃ ^- increased.     

Nitrogen Turnover and Nitrate Leaching after Bark Beetle Attack in Mountainous Spruce Stands of the Bavarian Forest National Park

More than 85% of the mountainous spruce forest of the Bavarian Forest National Park died after bark beetle attack during the last decade. The elemental budget of intact stands and of different stages after the dieback was investigated. N-fluxes in throughfall of intact stands were lower (12–16 kg ha^-1 a^-1) than in an earlier study in an intact mountainous spruce stand in the Bavarian Forest National Park and were reduced in the first years after the dieback (3–5 kg N ha^-1 a^-1). Nitrate-N fluxes by seepage water of intact stands at 40 cm depth, which is below the main rooting zone, were moderate (5–9 kg ha^-1 a^-1). After the dieback of the stands, NH₄ ⁺ concentrations were increased in humus efflux as were NO₃ ^- concentrations in mineral soil. Due to the relatively high precipitation, dilution of the elemental concentrations in seepage was considerable.Therefore, NO₃ ^- concentrations were usually below the level of drinking water (806 μmol NO₃ ^- L^-1), with lowest concentrations after the snowmelt and highest in autumn. Nitrate concentrations were elevated from the first year until the 7th year after the dieback. Total NO₃ ^--N losses by seepage until the 7th year after the dieback equalled 543 kg N ha^-1. Aluminium fluxesafter the dieback were enhanced in the mineral soil from 55 to 503 mmol_c m^-2 a^-1 (average of 8 yr), K⁺ fluxes from 8 to 37 mmol_c m^-2 a^-1, and Mg²⁺ fluxes from 13 to 35 mmol_c m^-2 a^-1. The consequences for the nutritional status of the ecosystem, the hydrosphere, and forest management are discussed in the paper.     

Study of Trace and Heavy Metals in Rural and Urban Aerosols of Uludağ and Bursa (Turkey)

The concentrations of heavy, trace elements and major ions measuredin the Uluda and Bursa aerosols were investigated to assess size distributions, spatial and temporal variability, sources and source regions affecting the composition of aerosols in Uluda and Bursa. A total of 81 samples were collected in two sites, one in Bursa city and another in the Uluda Mountain during two sampling campaigns. Daily samples were collected using a high volume sampler on Whatman 41 cellulose filters in Uluda, while three days interval samples were collected in Bursa using an automatic dichotomous sampler on PTFE Teflon filters. Samples were analysed for 15 trace and heavy metals (Al, Fe, Ba, Na, Mg, K, Mn, Ca, Cu), (V, Pb, Cd, Cr, Ni, Zn), and 4 major ions (SO₄ ^2-, NO₃ ^-, Cl^-), (NH₄ ⁺) using ICP-AES, GFAAS, HPLC and UV/VIS Spectrophotometer,respectively. In general, concentrations of the metals measured inUluda aerosols were lower than those in Bursa. The concentrations of crustal elements were higher in summer than winter, while anthropogenic elements had higher concentrations in winter than summer. Most of the mass of crustal elements was concentrated in the coarse mode while the mass of the heavy metals was concentrated in the fine mode. Factor analysis revealed four factors with sources including crustal, industrial and combustion. Back trajectory calculations were used to determine long range contributions. These calculations showed that contributions were mostly from European countries, former Soviet Union countries, Black Sea and North Africa.     

Trends in Water Chemistry in a Maple Forest on a Steep Slope

Year-to-year variation in SO₄ ^2-,NO₃ ^-, Ca²⁺, K⁺, and Mg²⁺concentrations in forest floor and mineral soil percolatefrom a forested, podzolic soil at the Turkey Lakes Watershedon the Precambrian Shield was assessed for monotonic trendsbetween 1986 and 1995. Our objective was to examine howrapidly ion concentrations in soil percolate equilibratedafter stabilization of SO₄ ^2- concentrations inprecipitation. Significant negative trends were detected inmonthly Ca²⁺, and Mg²⁺ concentrations in forestfloor and SO₄ ^2-, Ca²⁺, and Mg²⁺ inmineral soil percolate during the 10-year-period. Thedecline in Ca²⁺ and Mg²⁺ was greater than annualdecreases in SO₄ ^2- and NO₃ ^- in forestfloor percolate and proportional to the reduction inSO₄ ^2- in mineral soil percolate. Response ofmineral soil percolate to a 15 mol_c L^-1SO₄ ^2- decrease in wet-only precipitation between1985 and 1986 was a gradual decline in SO₄ ^2-concentration through 1995. The five-year meanSO₄ ^2- concentration in bulk precipitation, forestfloor percolate, and mineral soil percolate decreased 8, 9and 18 mol_c L^-1 from 1986–90 to 1991–95.Microbial (mineralization of organic S) and sorption(release from and/or retention in the pool of insolubleSO₄ ^2-) processes in the soil were logicalexplanations for the observed changes in SO₄ ^2- inmineral soil percolate.     

Nitrate Leaching From a Mountain Forest Ecosystem with Gleysols Subjected to Experimentally Increased N Deposition

Nitrate leaching was measured over seven years of nitrogen (N) addition in a paired-catchment experiment in Alptal, central Switzerland (altitude: 1200 m, bulk N deposition: 12 kg ha^-1 a^-1). Two forested catchments (1500 m² each) dominated by Picea abies) were delimited by trenches in the Gleysols. NH₄NO₃ was added to one of the catchments using sprinklers. During the first year, the N addition was labelled with ¹⁵N. Additionally, soil N transformationswere studied in replicated plots. Pre-treatment NO₃ ^--N leaching was 4 kg ha^-1 a^-1 from both catchments, and remained between 2.5 and 4.8 kg ha^-1 a^-1 in the control catchment. The first year of treatment induced an additional leaching of 3.1 kg ha^-1, almost 90% of which was labelled with ¹⁵N, indicating that it did not cycle through the large N pools of the ecosystem (soil organic matter and plants). These losses partly correspond to NO₃ ^- from precipitation bypassing the soil due to preferential flow. During rain or snowmelt events, NO₃ ^- concentration peaks as the water table is rising, indicating flushing from the soil. Nitrification occurs temporarily along the water flow paths in the soil and can be the source of NO₃ ^- flushing. Its isotopic signature however, shows that this release mainly affects recently applied N, stored only between runoff events or up to a few weeks. At first, the ecosystem retained 90% of the added N (2/3 in the soil), but NO₃ ^- losses increased from 10 to 30% within 7 yr, indicating that the ecosystem became progressively N saturated.     

Isotopic Assessment of Sources of Surface Water Nitrate within the Oldman River Basin, Southern Alberta, Canada

Concentrations and isotopic compositions of NO₃ ^- from the Oldman River (OMR) and some of its tributaries (Alberta, Canada) have been determined on a monthly basis since December 2000 to assess temporal and spatial variations of riverine NO₃ ^- sources within the OMR basin. For the OMR sites, NO₃ ^--N concentrations reached up to 0.34 mg L^-1, δ¹⁵N-NO₃ ^- values varied between –0.3 and +13.8‰, and δ¹⁸O-NO₃ ^- values ranged from –10.0 to +5.7‰. For the tributary sites, NO₃ ^--N concentrations were as high as 8.81 mg L^-1, δ¹⁵N-NO₃ ^- values varied between –2.5 and +23.4‰, and δ¹⁸O-NO₃ ^- values ranged from –15.2 to +3.4‰. Tributaries in the western, relatively pristine forested part of the watershed add predominantlyNO₃ ^- to the OMR with δ¹⁵N-NO₃ ^- values near +2‰ indicative of soil nitrification. In contrast, tributariesin the eastern agriculturally-urban-industrially-used part of the basin contribute NO₃ ^- with δ¹⁵N-NO₃ ^- valuesof about +16‰ indicative of manure and/or sewage derived NO₃ ^-. This difference in δ¹⁵N-NO₃ ^- values of tributaries was found to be independent of the season, but rather indicates a spatial change in the NO₃ ^- source, which correlates with land use changes within the OMR basin. As a consequence of tributary influx, δ¹⁵N-NO₃ ^- values in the Oldman River increased from <+3‰ to >+6‰ in the downstream direction (W to E), although [NO₃ ^--N] increased only moderately (generally <0.5 mg L^-1). This study demonstrates the usefulness of δ¹⁵N-NO₃ ^- and δ¹⁸O-NO₃ ^- values in identifying the addition of anthropogenic NO₃ ^- to riverine systems.     

Nutrients on Asphalt Parking Surfaces in an Urban Environment

Amounts of readily soluble nutrients on asphalt parking lot surfaceswere measured at four locations in metropolitan Phoenix, Arizona, U.S.A. Using a rainfall simulator, short intense rainfall events were generated to simulate `first flush' runoff. Samples were collected from 0.3 m² sections of asphalt at 8 to 10 sites on each of four parkinglots, during the pre-monsoon season in June-July 1998 and analyzed for dissolved NO₃ ^--N, NH₄ ⁺-N, soluble reactive phosphate (SRP), and dissolved organic carbon (DOC). Runoff concentrations varied considerably for NO₃ ^--N and NH₄ ⁺-N (between 0.1 and 115.8 mg L^-1) and DOC (26.1 to 295.7 mg L^-1), but less so for SRP (0.1 to 1.0 mg L^-1), representing average surface loadings of 191.3, 532.2, and 1.8 mg m^-2 respectively. Compared with similar data collected from undeveloped desert soil surfaces outside the city, loadings of NO₃ ^--N and NH₄ ⁺-N on asphalt surfaces were greater by factors of 91 and 13, respectively. In contrast, SRP loads showed little difference between asphalt and desert surfaces. Nutrient fluxes in runoff from a storm that occurred shortly after the experiments were used to estimate input-output budgets for 3 of the lots under study. Measured outputs of DOC and SRP were similar to those predicted using rainfall and experimentally determined surface loadings, but for NH₄ ⁺-N and particularly for NO₃ ^--N, estimated rainfall inputs and surface runoff were significantly higher than exports in runoff. This suggests that parking lots may be important sites for nutrient accumulation and temporary storage in arid urban catchments.     

Simulation of Nitrogen Dynamics and Fluxes in Contrasting Catchments in Norway by Applying the Integrated Nitrogen Model for Catchments (INCA)

The process-based INCA model was applied to Dalelva Brook (3.2 km²) and the Bjerkreim River (685 km²) including several subcatchments, in order to test the model's ability to simulate streamwater nitrate (NO₃ ^-) dynamics and output fluxes under highly contrasting climatic conditions and nitrogen (N) loading. The simulated runoff volumes and mean NO₃ ^- concentrations at Dalelva and Bjerkreimwere within +2 to +10% of the measured average during 1993–1995 (–19 to +31% within individual years). INCA to a great extent also reproduced the observed streamwater flow dynamics at both study sites (coefficient of determination, r ² > 0.70). Temporal variation of streamwater NO₃ ^- during 1993–1995 was captured quite well by the model, especially at small catchments with a distinct seasonal NO₃ ^- pattern (r ² = 0.46–0.68). At the Bjerkreim River outlet, the relationship were somewhat weaker (r ² = 0.26, p < 0.01). Despite a few situations where the model failed to capturethe streamwater NO₃ ^- dynamics, INCA proved to be a quite robust tool for simulating NO₃ ^- dynamics and output fluxes in the two study catchments.     

Monitoring Studies of Precipitation and Cap Cloud Chemistry at Holme Moss in the Southern Pennines

Weekly collections of samples of precipitation and hill cloudwater have been made at Holme Moss (530 m.a.s.l.) in the southernPennines covering a six-year period (1994–1999). In addition continuous meteorological measurements have been conducted at thesite for a five year period (1995–1999). The concentrations of major ions in the samples have been determined by ion chromatography. Analysis of ion concentrations as a function ofwind direction reveals that the ions with anthropogenic sources (SO₄ ^–, NO₃ ^–, NH₄ ⁺, H⁺) exhibit higher concentrations during easterly wind directions whilst the ions with predominantly marine origins (Na⁺, Cl^–, Ca⁺⁺, Mg⁺⁺, K⁺) have concentrations thatare not significantly dependant on wind direction. Precipitation and cloud deposition are strongly correlated to south-westerly wind directions with a secondary peak occurring for north-easterly directions. Fifty nine per cent of ion deposition by rain was found to occur during wind from the SSW to W sector.The average concentrations of ions in cloud water were found tobe much higher than those in rain (by factors of between 2.5 and4.2). It is thought that the high precipitation and annual deposition of ions by precipitation at Holme Moss is due in partto the enrichment of ion concentrations in precipitation by thescavenging of more concentrated cap cloud droplets (the `seeder-feeder effect'). Comparison with data from a nearby lower level site shows encouraging agreement with the scheme currently used in the U.K. deposition mapping procedure to incorporate the influence of orography on deposition by precipitation.     

Implications of Heterogeneous Chemistry of Nitric Acid for Nitrogen Deposition to Marine Ecosystems: Observations and Modeling

Size resolved particle composition and nitric acid (HNO₃)measurements from the ASEPS'98 experiment conducted in the BalticSea are used to provide observational evidence of substantialgas-particle transfer of oxidized nitrogen (N) compounds in themarine boundary layer. We then focus on the importance ofHNO₃ reactions on sea salt particles in determining spatio-temporal patterns of N dry deposition to marine ecosystems.Modelling results obtained assuming no kinetic or chemical limiton HNO₃ uptake and horizontally homogeneous conditions withnear-neutral stability, indicate that for wind speeds 3.5 – 10 ms^-1 transfer of HNO₃ to the particle phase to formparticle nitrate (NO₃ ^-) may decrease the N depositionvelocity by 50%. We extend this research using the CHEM-COASTmodel to demonstrate that, in a sulphur poor environment undermoderate wind speeds with HNO₃ concentrations representativeof those found in the marine boundary layer, inclusion ofheterogeneous reactions on sea spray significantly reducesmodelled NO₃ ^- deposition in the near coastal zone.     

Topographic Controls of Nitrogen,Sulfur, and Carbon Transport from a Tolerant Hardwood Hillslope

The lateral down-slope movement of water, NO₃ ^-, NH₄ ⁺, SO₄ ^2-, H⁺ and DOC through an ablation till was examined from 1987 to 1990 for a one hectaresoil catena on a steep hillslope with uniform forest cover at the Turkey Lakes Watershed (TLW), Ontario, Canada. Natural variation in the export of nutrients from the soil profile via soil water to Little Turkey Lake was assessed in relation to nutrient distribution in soil at different topographic positions.Subsurface throughflow exhibited dramatic differences in nutrientconcentrations and fluxes with slope position, largely reflectingthat of the soil horizons through which the water passed. GreaterNO₃ ^-, SO₄ ^2-, and DOC concentrations in subsurface water in the upper, well-drained hillslope were a reflection of enrichment by contact with more acidic, more developed podzols, and more favorable soil physical and biological conditions for NO₃ ^- retention in solution.Nutrient inputs to the lake were strongly influenced by increaseddown-slope transport of water, and increased SO₄ ^2-, N, and C retention in wetter, less-developed podzolic soils that characterize lower slope positions. An understanding of water movement and soil development variation withtopographic position was required to accurately estimate nutrient budgets for steep slopes at TLW.     

Fluxes of NO3-, NH4+, NO,NO2, and N2O in an Old Danish Beech Forest

The fluxes of the major nitrogen compounds havebeen investigated in many ecosystem studies over the world.However, only in few studies has attention been drawn to theimportance of the fluxes of minor gaseous nitrogen compoundsto complete the nitrogen cycle. In Denmark a detailed study onthe nitrogen cycle in an old beech forest has been implementedin 1997 at Gyrstinge near Sorø, Zealand. The study includesthe fluxes of the gases NO, N₂O and water mediatedtransport of NO₃ ^- and NH₄ ⁺. Measurementsof the fluxes of the gaseous compounds are performed withmicro-meteorological methods (eddy-correlation and gradient)and with chambers. Water mediated fluxes encompass rain,throughfall, stem-flow and leaching from the root zone. Thehydrological model is verified by TDR measurements. The findings show that the total water mediated N input tothe forest floor with throughfall and stemflow was 25.6 kg Nha^-1 yr ^-1, and open field wet deposition withprecipitation was 19.0 kg N ha^-1 yr ^-1. The internalcycling of N in the ecosystem measured as turnover oflitterfall and plant uptake was 100 kg N ha^-1 yr ^-1and 14 kg N ha^-1 yr ^-1, respectively. The fluxes ofthe gaseous N compounds NO and N₂O were of minorimportance for the total N turnover in the forest, NO_xemission being <1 kg N ha^-1 yr ^-1 and N₂Oemission from the soil being 0.5 kg N ha^-1 yr ^-1 withno significant difference between wet and dry soils.Concentrations of NO₃ ^- and NH₄ ⁺ in thesoil solution beneath the rooting zone are very small andconsequently the N leaching is almost negligible. It isconcluded that the nitrogen mass balance of this old beechforest ecosystem mainly is controlled by the input by dry andwet deposition and a large internal N cycle with a fast litterturnover. The nitrogen input tothe forest ecosystem which currently exceeds the critical loadby 5 kg N ha^-1 yr ^-1is mainly accumulated in the soil and no significant nitrateleaching is occurring.     

Effects of Acidification and its Mitigation with Lime and Wood Ash on Forest Soil Processes in Southern Sweden. A Joint Multidisciplinary Study

A joint multidisciplinary investigation was undertaken to studythe effects of lime and wood ash applications on two Norway spruce forest Spodosolic soils. The two sites, typical for southern Sweden, were treated in 1994 with either 3.25 t ha^-1 dolomite or 4.28 t ha^-1 wood ash (Horröd site) or in 1984 with either 3.45 or 8.75 t ha^-1 dolomite (Hasslöv site). Both sites show signs of acidification by atmospheric anthropogenic deposition and possessed low soil pH(4.3) and high concentrations of inorganic Al (35 M) in theupper illuvial soil solution. The prevailing soil conditions indicated perturbed soil processes. Following treatment with lime or wood ash, the soil conditions were dramatically altered. Cation exchange capacity (CEC) and base saturation (BS) was considerable increased after addition. Four years after application most of the added Ca and Mg was still present in the mor layer. Fifteen years after application,Mg in particular, became integrated deeper in the soil profile with a greater proportion lost by leaching incomparison to Ca. The concentrations of these ions were greatestin the mor layer soil solutions and Mg had higher mobility givinghigher concentrations also deeper in the profile. Four years after treatment, the application of wood ash and limeresulted in lower pH values and higher inorganic Al in mineral subsoil solutions compared to the untreated soil. We hypothesize that this was probably due to an increased flow of hydrogen ionsfrom the upper soil as a result of displacement by Ca and Mg ionsin the enlarged exchangeable pool. In contrast, fifteen years after lime and wood ash application, the mineral subsoil horizonspossessed a higher pH and lower soil solution Al content than theuntreated plots.Liming promoted soil microbial activity increasing soil respiration 10 to 36%. This is in the same range as net carbon exchange for forests in northern Sweden and could potentially have a climatological impact. The turnover of low molecularweight organic acids (LMWOA) by the soil microbial biomass werecalculated to contribute 6 to 20% to this CO₂ evolution.At Horröd, citrate and fumarate were the predominant LMWOAs with lowest concentrations found in the treated areas. In contrast, at the Hasslöv site, propionate and malonate were the most abundant LMWOAs. Higher microbial activity in the upper soil horizons was also theprobable cause of the considerably higher DOC concentrations observed in the soil solution of ash and lime treated areas. Thelime-induced increase in DOC levels at Hasslöv could be attributed to increases in the 3–10 kDa hydrophobic size fraction. Liming also promoted nitrification with high liming doses leading to extreme concentrations of NO₃ ^- (1 mM) in soil solution.At Hasslöv the community of mycorrhizal fungi was dramatically changed by the addition of lime, with only four of 24 species recorded being common to both control and treated areas.Many of the observed effects of lime and ash treatment can be viewed as negative in terms of forest sustainability. After fouryears of treatment, there was a decrease in the pH of the soil solution and higher concentrations of inorganic Al and DOC. Increased organic matter turnover, nitrification and NO₃ ^-leakage were found at Hasslöv. Considering that the weathering rate and the mineral nutrient uptake by trees is mostprobably governed by mycorrhizal hyphae etchingmineral grains in the soil, it is important to maintain this ability of the mycorrhizal fungi. The lime and ash-induced changed mycorrhizal community structure may significantly affect this capability. In light of this investigation and others, as reviewed by Lundström et al. (2003), the implications ofliming on forest health are multifaceted with complex relationships occurring over both space and time.     

Sulphate and Nitrate in Precipitation and Soil Water in Pine Forests in Latvia

The SO₄–S and NO₃–N concentrations and pH in bulk precipitation, throughfall, stemflow and soil water for the 1994–2004 period were studied in pine forests in Latvia (Rucava and Taurene Integrated Monitoring stations). The SO₄–S and NO₃–N concentrations decreased over the study period, simultaneously with a decrease of acidity in precipitation. The changes were more evident in the western part of Latvia, probably due to declining long-range air pollution from West Europe. The trend of decreasing sulphate concentrations and increasing pH in precipitation were not followed by respective changes in soil water. In the upper soil horizon sulphate ion concentrations and acidity increased in soil water. Over the observation period, nitrate concentrations also showed an increasing trend in soil water at Rucava and Taurene, but these changes were not statistically significant.     

Effects of Nitrogen Deposition on Bryophyte Species Composition of Calcareous Grasslands

Regular additions of NH₄NO₃ (35–140 kg N ha⁻¹ yr⁻¹) and (NH₄)₂SO₄ (140 kg N ha⁻¹ yr⁻¹) to a calcareous grassland in northern England over a period of 12 years have resulted in a decline in the frequency of the indigenous bryophyte species and the establishment of non-indigenous calcifuge species, with implications for the structure and composition of this calcareous bryophyte community. The lowest NH₄NO₃ additions of 35 kg N ha⁻¹ yr⁻¹ produced significant declines in frequency of Hypnum cupressiforme, Campylium chrysophyllum, and Calliergon cuspidatum. Significant reductions in frequency at higher NH₄NO₃ application rates were recorded for Pseudoscleropodium purum, Ctenidum molluscum, and Dicranum scoparium. The highest NH₄NO₃ and (NH₄)₂SO₄ additions provided conditions conducive for the establishment of two typical calcifuges – Polytrichum spp. and Campylopus introflexus, respectively. Substrate-surface pH measurements showed a dose-related reduction in pH with increasing NH₄NO₃ deposition rates of 1.6 pH units between the control and highest deposition rate, and a further significant fall in pH, of >1 pH unit, between the NH₄NO₃ and (NH₄)₂SO₄ treatments. These results suggest that indigenous bryophyte composition may be at risk from nitrogen deposition rates of 35 kg N ha⁻¹ yr⁻¹ or less. These effects are of particular concern for rare or endangered species of low frequency.     

Development of Stream Water Chemistry during Spring Melt in a Northern Hardwood Forest

The role of snowmelt and subsurface hydrology in determiningthe chemistry of a small headwater stream in the TurkeyLakes Watershed (TLW) was evaluated for the spring meltperiods 1992 to 1996. Spring runoff is the dominanthydrological event at the TLW each year. Processesoccurring within the snowpack during snowmelt wereprincipally responsible for the above-ground changes inchemical fluxes relative to bulk deposition (the effect ofwinter throughfall was minimal). Large changes in chemicalfluxes occurred below ground. Organic matter decomposition,weathering, nitrification, and element cycling are some ofthe more important below-ground processes that operateduring the snow accumulation and ablation season and controlthe composition of the water ultimately appearing in thestream. Maximum stream discharge was accompanied byelevated concentrations of H⁺, NO₃ ^-, K⁺,NH₄ ⁺, DOC, Al and Mn, but reduced levels ofCa²⁺, Mg²⁺, SO₄ ^2- and SiO₂. Theconcentration-discharge relationships were consistent withwater movement through and above the forest floor duringpeak discharge, a flowpath facilitated by rapid infiltrationof meltwater and the existence of a relatively impermeablelayer in the mineral soil creating a perched water table. Averaged over the five periods of snow accumulation andablation, it was estimated that pre-melt stream flow, andwater routed through the forest floor and through the uppermineral soil contributed 9, 28 and 63%, respectively, ofthe discharge measured at the outlet of the catchment. Theforest floor contribution would be greater at peak dischargeand at higher elevations. An end-member mixing modelestimated concentrations of SO₄ ^2-, NO₃ ^-,Cl^-, Ca²⁺, Mg²⁺, Na⁺ and Al that werecomparable to average values measured in the stream. Othervariables (NH₄ ⁺, H⁺, K⁺ and DOC) wereover-estimated implying retention mechanisms operatingoutside the model assumptions.     

Impact of Lime and Ash Applications on Soil Solution Chemistry of an Acidified Podzolic Soil

Soil solution samples were taken from two sites (Horröd and Hasslöv) in the south part of Sweden to evaluate how soil solution chemistry responded to different treatmentswith dolomite and wood ash. At Horröd, samples were taken four years after application of wood ash, 4.28 ton ha^-1 and dolomite, 3.25 ton ha^-1. At Hasslöv dolomite, 3.45 ton ha^-1 and 8.75 ton ha^-1 was applied and samples were taken 15 yr later. It was found that treatment with dolomite at one site (Hasslöv) resulted in higher pH values (<2 pH units) and higher nitrification. It was also found at this site that the total Al and the inorganic Al concentrations decreased with dolomite treatment. The Ca, Mg, DOC, Fe, SO₄ ^2- and Cl^- concentrations, mainly in the topsoil, were found to be higher at both sites, following dolomite treatment; Ca and Mg concentrations were 2–8 times higher (<820 M) than in controls (<70 M). Wood ash was found to have less impact. The PO₄ concentration in the O2 horizon at Hasslöv decreased due to dolomite-treatment. ANOVA (Analyse of Variance) and PLS (Partial Least Square) were used to evaluate the data from the two sites.     

Synthesis of Chitosan@activated Carbon Beads with Abundant Amino Groups for Capture of Cu(II) and Cd(II) from Aqueous Solutions

In this study, chitosan and bio-based activated carbon obtained from sugarcane bagasse biowaste were used for the synthesis of efficient sorbent for Cu(II) and Cd(II) ion via precipitation method. The prepared material was enriched with amino groups through grafting tetraethylenepentamine and tested for heavy metal remediation from water samples. The influence of pH was investigated showing optimum sorption at pH 6 for Cu(II) and Cd(II). Sorption tests, explained by means of the most common sorption models, evidenced that the best performances were reached pointing out the promising application of the prepared sorbent for water purification treatments: Uptake kinetics are relatively fast: the equilibrium was reached within 140 min; and the kinetic profiles were preferentially fitted by the pseudo-second order rate equation. Sorption isotherms are fitted by Langmuir equation. The sorbent showed high metal ion sorption capacity with negligible influence of ion strength. The maximum sorption capacities reached 3.44 and 2.38 mmol g^??1 for Cu(II) and Cd(II), respectively at 298 K. Thermodynamic parameters were evaluated through variation of temperature. The sorption is unfavorable at elevated temperatures. Metal ions were successfully desorbed using 1 M HNO₃ solution.     

Temporal Trends in Water Chemistry in the Turkey Lakes Watershed Ontario,Canada, 1982-1999

The Turkey Lakes Watershed (TLW) was established in 1980 as asite for study of the ecosystem effects of acidic deposition, andsince then there has been 40% reduction in North AmericanSO₂ emissions. Monitoring records for bulk deposition,shallow and deep ground water, two headwater streams and two lakeoutflows have been tested to identify statistically significantmonotonic trends. The TLW appears to be responding to decliningacidifying emissions because the most prevalent chemical trendacross sample types/stations was decreasing SO₄ ^2-. Increasing pH was detected in four of the seven data sets, butonly the H⁺ decrease in bulk deposition was of a magnitudeto be an important ionic compensation for the SO₄ ^2-decline. There is little evidence of acidification recovery inTLW waters however. Increasing alkalinity was found only in theoutflow of the penultimate lake of the basin, and in fact, deepground water and the other lake outflow had decreasing alkalinitytrends (i.e., continuing acidification). For the surface waterstations, the greater part of the ionic compensation fordeclining SO₄ ^2- was decreasing base cations, and as aresult, these waters are probably becoming more dilute with time,although only the headwater streams exhibited decliningconductivity. Five of seven data sets had increasing dissolvedorganic carbon concentrations. Increasing NO₃ ^- wasimportant in ground waters. Drought has strongly influencedtrends and delayed recovery by mobilizing S stored in catchmentwetlands and/or soils.