Temporal variation in aluminum speciation and concentration during snowmelt

Precipitation samples in Alberta were collected and analyzed monthly from six Alberta Environment stations. Samples were collected with Sangamo samplers and analyzed for the major ions, pH and acidity. The data were tabulated and analyzed for spatial distribution, seasonal variation, temporal trends, ionic character and wet sulphate deposition. The major ionic species in Alberta precipitation are Ca²⁺, SO _inf4 ^sup2? , NH _inf4 ^sup+ and N0 _inf3 ^sup? . The spatial distribution shows a slight decrease in pH from southern Alberta (pH 6.0) to northern Alberta (pH 5.4). The seasonal variation shows higher hydrogen ion content in the summer months (pH 5.4 in summer and pH 5.8 in winter). Temporal trends are not apparent over the five year period investigated. The five year average wet sulphate deposition rate in Alberta is 9.1 kg ha^?1 yr^?1.     

Chemical Composition of Precipitation, Throughfall and Soil Solutions at Two Forested Sites in Guangzhou, South China

Rain water at two forested sites in Guangzhou (south China) show high concentrations of SO₄ ^2?, NO₃ ^? and Ca²⁺ and display a remarkable seasonal variation, with acid rain being more important during the spring and summer than during the autumn and winter. The amount of acid rain represents about 95% of total precipitation. The sources of pollutants from which acid rain developed includes both locally derived and long-middle distance transferred atmosphere pollutants. The seasonal variation in precipitation chemistry was largely related to the increasing neutralizing capacity of base cations in rainwater in winter. Soil acidification is highlighted by high H⁺ and Al³⁺ concentrations in soil solutions. The variation in elemental concentration in soil solution was related to nitrification (H⁺, NH₄ ⁺ and NO₃ ^?) and cation exchange reaction (H⁺, Al³⁺) in soil. The negative effect of soil acidification is partly dampened by substantial deposition of base cations (Ca²⁺, Mg²⁺ and K⁺) in this area.     

Nutrient content of precipitation over Iowa

Nutrient content and pH of precipitation samples collected at six sites during 1971–1973 were studied to determine the fraction of rainfall and snowmelt and the amounts of N, S, and P added by precipitation over Iowa The amount of NH₄-N ha^?1 added by precipitation annually at each site was about equal to that added as N0₃-N. The amounts of inorganic N ha^?1 yr^?1 added ranged from 10 kg in north-central to 14 kg in west-central Iowa, and the annual amounts of S0₄-S ha^?1 added ranged from 13 kg in northeastern to 17 kg in north-central Iowa. It is estimated that, on average, precipitation adds about 0.6 kg of NH₄-N, 0.6 kg of N0₃-N, and 1.5 kg of S0₄ -S ha^?1 monthly in Iowa. However, the data indicated that, on an annual basis, the contribution of precipitation to P in soil is very small; at the most, about 0.1 kg of water-soluble P0₄-P ha^?1 was added annually in Iowa. No N0₂-N could be detected in any of the precipitation samples analyzed. Average pH value of the rainfall and snowmelt samples collected at each site during each year was about 6, individual samples seldom reached as low as pH 4. The data indicate that the concentration of S0₄-S in precipitation in this region is seasonal, high during fall and winter and low during spring and summer.     

Seasonal variation of radon daughters in outdoor air in Montreal

The concentration of Rn daughters in outdoor air in Montreal was measured 222 times over a 1 yr period from April 1988 to March 1989. The values measured display a mean of 4.4 Bq m^?3, a median of 2.6 Bq m^?3, a mode of 2.2 Bq m^?3 and a standard deviation of 4.4 Bq m^?3. The concentrations show a pronounced seasonal variation. They are highest in summer and lowest in winter. It is believed that this behavior is due to the cold climate. The histogram of concentrations has a coefficient of skewness of 2.3 and a coefficient of kurtosis of 9.7.     

Zusammensetzung und Speziierung der Bodenlösung eines mit Schwermetallen belasteten kalkreichen Bodens

Composition and Speciation of Soil Solution collected in a Heavy Metal polluted calcareous Soil Close to a brass foundry, which had emitted heavy metal containing dusts for over 80 years, soil water was collected in the topsoil (18 cm) and in the subsoil (40 cm) of a severely polluted Calcic Fluvisol by means of polyethylen suction cups over a period of 2 years. The total metal content of the topsoil (extracted with 2M HNO₃ at 100 °C for 2 hours) was 38 nmol g^?1, 24 μmol g^?1, and 25 μmol g^?1 for Cd, Cu, and Zn, respectively. The mean heavy metal concentrations of the soil solution were 0.5 mol L^?1, 300 nmol L^?1, and 200 nmol L^?1 in the topsoil and 0.6 nmol L^?1, 90 nmol L^?1, and 30 nmol L^?1 in the subsoil for Cd, Cu, and Zn, respectively. Solubility calculations showed that the soil solutions were undersaturated with respect to heavy metal carbonates as well as to hydroxides. It seems that the heavy metal concentration is determined by sorption processes rather than by precipitation. The composition of the soil solution has been shown to be governed by the presence, of calcite, by the soil temperature and by the partial pressure of CO₂ in the soil air. The pCO₂ in the soil air (in both depths) has been estimated at 2 mbar during the winter term and at 20 mbar during the summer term. A corresponding increase of the concentration of macroelements (Ca, Mg, Na) as well as of total dissolved carbonate and of dissolved organic matter (DOC) has been measured in the summer half year. No significant seasonal variations of the heavy metal concentrations were detected and no correlations with concentrations of other components could be found.     

The influence of storm characteristics on sulfate in precipitation

The effects of storm dynamics on precipitation chemistry were examined using an atmospheric budget for SO₄ ^? . One hundred storms occurring between 1975 and 1978 at Hubbard Brook Experimental Forest in New Hampshire were used as test data. Concentrations of major ions were usually greater in convective storms than in continuous or layer storms. For example the geometric mean concentrations of SO₄ ^? in convective and continuous storms were 4.1 and 1.1 mg L^?1, respectively. Higher SO₄ ^? concentrations also occurred when surface wind directions were south or southwest. The summer maximum in convective activity along with the seasonal dependence of surface wind directions and the seasonal atmospheric chemistry cycle can account for the summer maximum in SO₄ ^? concentrations observed in the northeastern United States.     

Chemical composition of precipitation in a forest area of Chongqing,Southwest China

Experiments were carried.out in Chongging-a city seriously damaged by acid precipitation in southwest China — to explore chemical compositions of open bulk precipitation, throughfall and stemflow in a Masson pine (Pinus massoniana) forest. The results showed that annual mean pH values of and annual ion depositions in the three types of rain water were 4.47 and 50.6 g m^?2, 3.82 and 69.7 g m^?2, and 2.92 and 0.215 g m^?2 respectively. pH values demonstrated an obvious seasonal variation; they were lower in winter than in the rest of the year. Ca²⁺ and NH _inf4 ^sup+ together made up more than 80% of the total cation, while SO _in4 ^sup2? alone contributed over 90% to the total anion. This high level of SO _in4 ^sup2? in rain water in Chongqing, which outran those found in other cities in China, was closely related to the combustion of locally produced coal that contains 3 to 5% sulphur. Thus, acid precipitation in Chongqing is of a typical sulphuric-acid type.     

Seasonal variations of oil residues in water of Shatt al-Arab river,Iraq

The distribution and seasonal variations of petroleum residues in the Shatt al-Arab water column have been determined spectrofluorometrically. Their concentrations were found to vary between 1.7 to 35.4 μg L^?1 Kuwait crude oil equivalents. The results suggested that petroleum hydrocarbons present in this river originated from diverse sources. Hydrocarbon amounts tend to be highest in winter (averaged 17.4 μg L^?1) and lowest in summer (averaged 3.1 μg L^?1).     

Influence of the Sampling Period on the Deposition Time Series of Major Ions in Bulk Precipitation

The influence of a change from daily to weekly sampling of bulk precipitation on the obtained deposition values was studied with parallel sampling for 8 months at the station of Virolahti in 2004. Due to dry deposition, the deposition values of the whole period were found to be 5–70% higher from weekly sampling than from daily sampling, the biggest difference being for K⁺, Ca²⁺, Mg⁺ and Na⁺. The collection efficiencies of the summer sampler and the winter sampler compared to the standard rain gauge were studied from daily sampling in 1991–2003 and weekly sampling in 2004–2008. The performance was best in summer and in winter with rain samples (median value 85–88%), while the median value for daily snow samples was 72%. In winter, the total sum of precipitation collected in the daily sampler and the weekly sampler was 78% and 69%, respectively. The deficit in the weekly sampler in winter was concluded to be due to evaporation, while from the summer sampler no evaporation seemed to occur. Use of the precipitation amount measured by the standard rain gauge when calculating annual precipitation-weighted mean values gave higher mean concentrations than the use of the precipitation measured by the deposition sampler itself, the biggest difference of 8–11% being in the sea-salt ions Cl^?, Mg⁺ and Na⁺. It was concluded that the concentration and deposition values measured by daily and weekly bulk sampling are incompatible, and should not be combined into the same time series.     

Acid Deposition and Acidification of Soil and Water in the Tie Shan Ping Area, Chongqing, China

Chongqing is among the heaviest polluted cities in China. Combustion of coal with relatively high sulfur content causes high sulfur emission and deposition in the area. Effects on soils and waters of the acid deposition in the Chongqing area have been studied in the field at a forested site outside the city. Deposition chemistry and fluxes, soil and soil water chemistry as well as surface water chemistry are presented for the period 1996–1998. There are some stress symptoms at the forest in the area and severe forest damage has been reported at Nanshan, closer to Chongqing center. Monitoring of the acidification situation in the area must be followed closely as impacts may be expected if the deposition is not reduced in the future. The deposition of sulfur, H⁺ as well as calcium at the site is high. Wet deposition of sulfur is estimated to 4.7 – 5.7 g S m^?2 yr^?1 during the three years sampled; dry deposition is probably of similar size. Annual volume-weighted pH in bulk deposition was 4.0 – 4.2 and the calcium wet deposition flux was 2.6 – 3.6 g Ca²⁺ m^?2. There are considerable seasonal variations in the concentrations, related to the seasonal variations in precipitation amount (dry winter, wet summer). The soils at the site are acid with median base saturation of 12% and 8% in the topsoil and subsoil, respectively. In soil water, aluminum concentrations are typically in the range 3–8 mg L^?1. However, due to the high base cation deposition, the Al/(Ca²⁺+Mg²⁺) molar ratio is below unity in most samples, indicating little damage of forest due to aluminum in soil water.     

Element Inputs and Canopy Interactions in two Pine Forest Ecosystems in Berlin,Germany

For 3 years (1986-89), element fluxes with bulk deposition and throughfall were determined in a 40 yr. old pine plantation and a 80-140 yr. old mixed pine/oak stand in the Grunewald forest in Berlin. Although SO₄-inputs are very high (60 kg S·ha^?1.a^?1) due to the urban character of the study site, acid inputs are moderate because of the buffering action of airborne alkaline dusts. This is reflected in the high Ca-inputs (12 kg·ha^?1a^?1 in bulk precipitation). Acid neutralisation was also observed in the canopies and could be attributed to 60-80% to increased Ca- and Mg-fluxes in throughfall, stemming from foliage leaching and dust interception. Heavy metal inputs were low in comparison to other Central European study sites, the decrease in Pb-inputs over the 3-year period could be attributed to the increased use of unleaded gasoline since 1987. Total inputs and canopy leaching showed clear seasonal patterns for some elements: SO₄-, H-, Ca- and Mg-fluxes were higher in winter, on the other hand, K- and Mn-enrichment in throughfall showed two peaks, in early summer and late fall.     

Behavior of iodine in a forest plot,an upland field and a paddy field in the upland area of Tsukuba,Japan: Seasonal variations in iodine concentration in precipitation and soil water and estimation of the annual iodine accumulative amount in soil horizons

Abstract

In the course of a series of studies conducted to investigate the long-term behavior of ¹²⁹I (which has a half-life of 16 million years) in the environment, seasonal variation in the concentration of stable iodine (¹²⁷I) in precipitation and soil water to a depth of 2.5 m in a forest plot, an upland field and a paddy field in the upland area of Tsukuba, Japan, were determined. Iodine concentration in precipitation tended to increase during the summer (high air temperature) season and low-rainfall period, and a positive high correlation was observed between annual rainfall and the annual amount of iodine supplied by precipitation. No seasonal variations in iodine concentration in soil water were observed at any depth in the forest plot and upland field unlike at shallow depths (0.2 and 0.5 m) in the paddy field. In the paddy field, from the beginning of summer irrigation, under flooding conditions, iodine concentration in soil water at shallow depths (0.2 and 0.5 m) continuously increased, and immediately before mid-summer (intermittent) drainage and drainage, the maximum iodine concentration (approximately 50 µg L^?1) and lowest E_h values (approximately ?150 to ?200 mV) were recorded. These high iodine concentration levels and low E_h values were ascribed to high air temperature (approximately > 25°C on average every 10 days) and the continuation of the groundwater level above the ground surface. As for the temporary winter irrigation period (mean daily air temperature 2?4°C), the iodine concentration was low (1.7–3.7 µg L^?1) at all depths, as was the case in the non-irrigation period. After mid-summer drainage, and drainage, the iodine concentration in soil water at depths of 0.2 and 0.5 m decreased drastically as the groundwater level decreased. The mean annual amount of iodine accumulated in the surface soil horizons (0–0.67 m) in the forest plot was estimated to be approximately 2.9 mg m^?2 (7.5 µg kg^?1 dry soil), which coincided with the mean annual amount of iodine supplied to the earth surface by precipitation. A mildly oxidative subsurface 2Bw horizon (0.60–0.89 m) in the paddy field was estimated to illuviate approximately 3.1 mg m^?2 (20 µg kg^?1 dry soil) of iodine annually by retaining iodine in the soil water percolated to this horizon.     

Seasonal,annual and long-term variability in the water chemistry of a remote high mountain lake: Acid rain versus natural changes

Seasonal fluctuations as well as long-term trends in water chemistry were studied in Schwarzsee ob Sölden (Tyrol, Austria), an oligotrophic softwater lake situated at 2796 m a.s.l. The catchement is composed of granite, plagioclase and micaschists containing considerable amounts of sulphur, with little soil cover. The lake is ice covered for about nine months, during this time the deepest layers (>16m) become anoxic. During summer overturn, alkalinity (ALK) is lowest (?8 μeq l^?1) in the whole water column, whereas pH reaches its minimum (4.88) at the surface during snowmelt. A decrease of pH from 5.8 to 5.4 during winter is caused by CO₂ oversaturation, but deep water ALK increases to up to 130 μeq l^?1 due to in-lake ALK generation by reductive processes and base cation (BC) release. The seasonal pattern of ALK in SOS is driven by in-lake processes in winter, the snowmelting in spring and watershed processes and precipitation during summer. Since 1989 summer sulfate concentrations in SOS, originating mainly from the catchment, show a tendency to increase presumably caused by enhanced weathering. In contrast, SO₄ ^2? concentrations in other high mountain lakes which are dominated by atmospheric depositions show a decreasing trend. SOS is a good example for the complexity of interactions between catchment and in-lake processes which act at different time scales and depend on climate changes and atmospheric inputs.     

Temporal and Elevation-Related Variability in Precipitation Chemistry from 1993 to 2002, Eastern Erzgebirge, Germany

The Erzgebirge, part of the so-called former “Black Triangle”, used to represent the strongest regional air pollution of Central Europe. To test the hypothesis of deposition enhancement with height, an altitudinal gradient along a N-S transect from the Elbe river lowlands to the Erzgebirge summit was chosen to investigate chemical composition, elevation-related variability, temporal changes, and seasonal patterns of ion concentrations from 1993 to 2002. The following questions were to be answered: (1) Which role does orography play on the composition of precipitation?, (2) Does fog occurrence overrule the orographic influence?, (3) Are there changes in the past 10 years, and if so, why?, (4) Do relevant seasonal changes occur and why? Air streams from westerly and to a lesser degree south-easterly directions prevail. The average precipitation was ion-poor (23 μS cm^?1 and acidic (pH 4.5). Sulphate still was the dominant anion (52.3–59.9 μeq L^?1, while NH⁺ ₄ determined the cations (41.9–62.2 μeq L^?1. Ion concentrations decreased with altitude to about 735 m a.s.l. and subsequently increased. The seeder-feeder effect largely explains the chemical composition of precipitation; enhanced in winter through snow crystals. Sub-cloud scavenging does not explain the observed patterns. Fog occurrence enhanced the observed effects at higher altitudes. Deposition amounts doubled from the lowlands to the Erzgebirge summit. From 1993 to 2002, acidity decreased by about 50%, mainly due to reduced SO₂ -emissions.     

Efficacy of different temperate pasture species to reduce nitrogen leaching from cattle urine applied in different seasons: A soil lysimeter study

A soil lysimeter field study assessed the efficacy of different pasture species to reduce nitrogen (N) leaching loss from cow urine deposited in different seasons. A single application of cow urine (¹⁵N‐labelled; equivalent to 622 kg N ha^?1) was applied in three different seasons (summer, autumn or winter) to three pasture species monocultures (perennial ryegrass, plantain or lucerne) on a free‐draining volcanic soil and monitored over 362 days. Leachate analyses revealed consistently large leaching losses of inorganic‐N from lucerne (>200 kg N ha^?1) across different urine application times due to the relatively low plant growth rates during winter (<15 kg DM ha^?1 day^?1) that led to low total recovery of urine‐N by lucerne plants (<20% of the applied urine‐¹⁵N). Conversely, plant uptake of the urine‐N was higher by plantain (ranging from 30% to 45% of that applied) driven by moderately higher winter plant growth rates (30 to 60 kg DM ha^?1 day^?1). Plantain exhibited large seasonal variation in its efficacy to reduce urine‐N leaching relative to ryegrass (ranging from 15% to 50% reduction for summer or winter urine applications, respectively) with an overall reduction of 39% in the total amount of inorganic‐N leached across the three seasons (53 vs. 87 kg N ha^?1 leached relative to ryegrass). This study has demonstrated the potential benefit of using plantain to reduce N leaching losses from urine deposited in the summer to winter grazing period. However, further research is required to quantify the effects of plantain on annual N leaching losses from grazed pastoral systems.     

Atmospheric monitoring network operations and results in Canada

Atmospheric monitoring activities in Canada relevant to the long-range transport of atmospheric pollutants and the ‘acid rain’ problem are reviewed. Particular aspects examined are network objectives, station density and location, sampling protocol, and quality assurance. Results from a number of these networks are presented for the purpose of outlining the nature and extent of air and precipitation contamination by pollution released in eastern North America. Examples discussed include: the spatial distribution of acidic wet deposition, the temporal variation of acid-related substances in both air and precipitation, an episode of long-range transport, and the impact of acidic emissions on the Arctic atmosphere. Acidic wet deposition is greatest in Canada east of the Manitoba-Ontario border. In 1978, it ranged from 18 to 46 mmol H⁺ m^?2 yr^?1 in the southern half of eastern Canada, with maxima in southern Ontario (44 mmol H⁺ m^?2 yr^?1) and southwestern Quebec (46 mmol H⁺ m^?2 yr^?1). Western Canada receives less acidity in precipitation, but areas of some concern are the Pacific Coast (10 mmol H⁺ m^?2 yr^?1) and to a lesser extent northern Alberta and Saskatchewan (3 to 5 mmol H⁺ m^?2 yr^?1). Acidic emissions from mid-latitude sources which reach the Arctic in winter cause an increase in the acidity of snow from a pH of approximately 5.6 in the summer to values of 4.9 to 5.1 in January through March.     

Hydrogen ion input to the hubbard brook experimental forest,New Hampshire,during the last decade

Being downwind of eastern and midwestern industrial centers, the Hubbard Brook Experimental Forest offers a prime location to monitor long-term trends in atmospheric chemistry. Continuous measurements of precipitation chemistry during the last 10 yr provide a measure of recent changes in precipitation inputs of H ion. The weighted average pH of precipitation during 1964–65 to 1973–74 was 4.14, with a minimum annual value of 4.03 in 1970–71 and a maximum annual value of 4.21 in 1973–74. The sum of all cations except H ion decreased from 51 μeq 1^?1 in 1964–65 to 23 μeq 1^?1 in 1973–74 providing a significant drop in neutralizing capacity during this period. Based upon regression analysis, the input in equivalents of H ion and nitrate increased by 1.4-fold and 2.3-fold respectively, from 1964–65 to 1973–74. Input of all other ions either decreased or showed no trend. Based upon a stoichiometric formation process in which a sea-salt, anionic component is subtracted from the total anions in precipitation, SO₄ ⁼, contribution to acidity dropped from 83% to 66%, whereas NO₃ ^? increased from 15% to 30% during 1964–65 to 1973–74. The increased annual input of H ion at Hubbard Brook during the past 10 yr is highly correlated with the increased input of nitrate in precipitation.     

Occurrence and turnover of atmospheric mercury over the nordic countries

A seasonal variation of both particle and gaseous Hg concentrations in the atmosphere is present in south-western Sweden. An average gaseous Hg level of 3.7 ng m^?3 is found in winter, compared to 2.8 ng m^?3 in summer. A weak decreasing south-north gradient for gaseous Hg in air over the Nordic countries is also present, with yearly average values from 3.2 to 2.8 ng m^?3. A gradient for particulate Hg is less clear. An air parcel trajectory sector classification of gaseous Hg levels in air, and to some extent the particulate associated Hg, clearly demonstrates the increased concentrations in the southern sectors, especially in south-western Sweden where the gaseous Hg increase is about I ng m^?3. These observations are consistent with an influence from the European continent. The average concentrations of Hg in precipitation at the various stations show a pronounced decreasing south-north gradient. A major portion of the total Hg present in precipitation is associated with particles. For the southern stations, a strong correlation between Hg and sulfate, or pH, is present suggesting a connection between Hg in precipitation and anthropogenic activities.     

Examining the Relationships Between the Activities of 3H in Precipitation and 137Cs in Ground-Level Air in Belgrade City Area

Specific activity of tritium (³H) in precipitation and specific activity of ¹³⁷Cs in ground-level air were monitored at three locations in Belgrade (Meteorological Station of Belgrade at Zeleno Brdo (ZB), Meteorological Station Usek (USEK), and Vin?a Institute of Nuclear Sciences (VINS)). Data presented cover the period 1985?C1997 for ¹³⁷Cs for all locations and 1985?C2009 (ZB), 1988?C1997 (USEK), and 1988?C2009 (VINS) for ³H. Concentrations of ³H in precipitation have been determined using electrolytic enrichment and liquid scintillation spectrometer LKB-Wallac 1219 RackBeta. The activity of ¹³⁷Cs in air was determined on an HPGe detector (Canberra, relative efficiency 23?%). ³H concentrations in precipitation ranged from 0.40?±?0.08 to 74.6?±?5.2?Bq?l^?1 decreasing with distance from the nuclear facilities. Significantly higher tritium levels were measured in samples in VINS compared with those from an off-site location. The observed seasonal variations of tritium concentration indicate the stratospheric source of tritium. Increases in activity concentration of ¹³⁷Cs in the atmosphere were observed after the nuclear plant accident at Chernobyl in April 1986. The concentrations obtained for ¹³⁷Cs in 1986 were compared with the integrated air concentrations of ¹³⁷Cs in the region. The increases of ¹³⁷Cs air concentrations in 1987 and 1988 were attributed to local resuspensions from the ground. Since 1989, the activity level before the accident has been obtained. The average monthly concentrations of ¹³⁷Cs in ground-level air were shown spread maximum in spring?Csummer period and pronounced maximum during winter. The obtained results were statistically analyzed, i.e., the following parameters were determined: tritium deposition, monthly activities of ³H and ¹³⁷Cs, seasonal indices, radionuclide loading indices, and linear correlation coefficients.     

Airborne transport of sulphur: Impacts on chemical composition of rivers on north shore of the St. Lawrence River (Québec)

The St. Lawrence North Shore region (Québec) is subject to acid precipitation entailing sulphate deposition (17 to 22 kg SO₄ ^2? ha^?1 yr^?1) which poses a threat to sensitive aquatic ecosystems. Physicochemical surveys conducted in 1982–1983 revealed the extreme sensitivity of the region owing to weak mineralization of the waters (mean alkalinity of 55 μeq L^?1 and conductivity of 17 μS cm^?1). Calculation of the annual loads of S discharged from 21 rivers throughout the region shows atmospheric deposition as the principal source of sulphate. A decreasing west-east gradient in the concentration is interpreted in terms of the impact of long-range airborne transport, although certain local sources of S emission are not to be overlooked. Analysis of the seasonal variation in the sulphate load balance, conducted in a small drainage basin (40 km²), revealed that the sulphate anion plays a part in lowering the water pH in spring. The spring pH depression is apparently intensified by an additional input of sulphate stemming from the release of this element subsequent to accumulation in the drainage basin during summer and fall. Organic acids play a measurable role in the chemical equilibrium of surface waters in the region, particularly in the eastern sector where there is less S fallout. Low pH levels in this sector (5.5 to 6.0) point to some degree of organic acidification.