Chemistry of Dissolved Organic Carbon at Bear Brook Watershed, Maine: Stream Water Response to (NH4)2SO4 Additions

This study was conducted to determine the response of stream water DOC and organic acidity to increased inputs of ammonium sulfate to a whole catchment. Precipitation, throughfall, soil solutions (from Spodosols) and stream waters were characterized for DOC concentrations and fractions (hydrophobic acids and neutrals, hydrophilic acids, bases, and neutrals) in both the control (East Bear) and the treatment (West Bear) catchments of Bear Brook Watershed, Maine (BBWM), a northern hardwood forest. In all solutions except precipitation, DOC was composed primarily of organic acids, with hydrophobic acids dominating (> 60% of DOC) in forest floor leachates (5000 mol C L-1), and a balance of hydrophobic and hydrophilic acids in deep B horizons and stream waters ( 150 mol C L-1). Stream waters had higher concentrations of DOC during storm or snowmelt events (high discharge), often reaching 300 to 400 mol C L-1. Forest floor leachate C was rapidly attenuated by the mineral soils under all flow conditions, indicating how important mineral soil sorption of DOC was in reducing the loss of C via surface water from BBWM. No differences occurred between control and treatment streams for concentration or composition of DOC due to treatment from 1989 through 1994. In 1995, West Bear Brook had much lower concentrations of DOC than East Bear for the first time. However, this occurred during a year of record low runoff, suggesting that hydrology may have affected export of C. Average annual export of DOC from the catchments was similar (1000 to 2000 mol C ha-1 yr-1). Organic anions in streamwaters increased slightly during high flow events (e.g., East Bear had means of 15 and 19 eq L-1 organic anions during base flow and high discharge in 1995). Treatment of West Bear caused a decrease in organic anions, both in concentration and contribution to overall anion composition (organic anions during high discharge as a percentage of total anions decreased from about 8 to 4% for 1987-89 and 1993-95 samples, respectively). This was probably due to decreased solution pH (greater protonation of organics) and higher concentrations of inorganic anions. Overall, there were no clear, detectable changes in stream water DOC, with only minor changes in organic anions, as a result of treatment with ammonium sulfate.     

Seasonal characteristics of SO2, NO2, and CO emissions in and around the Indo-Gangetic Plain

Anthropogenic emissions of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and carbon monoxide (CO) exert significant influence on local and regional atmospheric chemistry. Temporal and spatial variability of these gases are investigated using surface measurements by the Central Pollution Control Board (India) during 2005–2009 over six urban locations in and around the Indo-Gangetic Plain (IGP) and supported using the satellite measurements of these gases. The stations chosen are Jodhpur (west of IGP), Delhi (central IGP), Kolkata and Durgapur (eastern IGP), Guwahati (east of IGP), and Nagpur (south of IGP). Among the stations studied, SO₂ concentrations are found to be the highest over Kolkata megacity. Elevated levels of NO₂ occur over the IGP stations of Durgapur, Kolkata, and Delhi. Columnar NO₂ values are also found to be elevated over these regions during winter due to high surface concentrations while columnar SO₂ values show a monsoon maximum. Elevated columnar CO over Guwahati during pre-monsoon are attributed to biomass burning. Statistically significant correlations between columnar NO₂ and surface NO₂ obtained for Delhi, Kolkata, and Durgapur along with very low SO₂ to NO₂ ratios (≤0.2) indicate fossil fuel combustion from mobile sources as major contributors to the ambient air over these regions.     

NH4NO3-Pd(NO3)2联合基体改进剂石墨炉法测海水中痕量镉

用NH4NO3-Pd(NO3)联合基体改进剂,石墨炉法直接测海水中痕量镉.通过不同条件的实验,确定了最佳的分析条件;并通过对实际样品平行性和加标回收率的测定,验证了方法的精密度和准确度.建立了空白实验,在0.19～5.0μg/L线性范围内,镉的最低检出限为0.19μg/L.实验结果表明,该方法快速方便,提高了分析效率,准确度高,精密度好.     

Chemical composition of the NH3-HNO3-H2SO4-NaCl system in the atmosphere of Athens,Greece

This paper presents a procedure for estimating the distribution of ionic material in the NH₃-HNO₃-H₂SO₄-NaCl system and applies this procedure in a particular case. The data used were measurements of HNO₃, NH₃, NO ₃ ^– , SO ₄ ^– , NH ₄ ⁺ Cl^– and Na⁺ performed during February 1989 – February 1990 in a central Athens street with high traffic density. According to the procedure, ions combine in the following manner: Na⁺ combines preferentially with SO ₄ ^– , then with NO ₃ ^– , followed by NH ₄ ⁺ with the remaining SO ₄ ^– and then with the remaining NO ₃ ^– to form bisulphates, sulphates and nitrates. The combination procedure showed that the main constituents of the NH₃-HNO₃-H₂SO₄-NaCl system are primarily (NH₄)₂SO₄ and, to a lesser extent, NH₄NO₃ and NH₄HSO₄, with mean and maximum concentrations, during morning hours, (NH₄)₂SO₄: 14.5 (max 46.8), NH₄NO₃: 2.97 (max 23) and NH₄HSO₄: 1.78 (max 40.6) µg m^–3. Lower concentations of Na₂SO₄, NaHSO₄, NaNO₃ and NH₄Cl and very low concentrations of H₂SO₄ are also present, depending on the availability of NaCl. It became apparent from the ionic distribution that there is sufficient NH₃ to neutralize the H₂SO₄ and HNO₃. It was also shown that a significant fraction of the HNO₃, especially on days with high pollution, occurs as aqueous NO ₃ ^– . A number of empirical equations have been proposed, which enable the approximate estimation of the constituents of the NH₃-HNO₃-H₂SO₄-NaCl system from air pollution monitoring data and meteorological parameters.     

Soil Type and Forest Vegetation Influences on Forest Floor Nitrogen Dynamics at the Bear Brook Watershed in Maine (BBWM)

The paired watershed experiment at the Bear Brook Watershed in Maine (BBWM) provided an opportunity to study changes in forest soil O horizon properties as a result of experimental, chronic N additions. The West Bear brook watershed received elevated N and S inputs since November 1989 as bimonthly applications of (NH4)2SO4. Forest floor samples (O horizon) were collected in July of 1992 from three dominant stand and five soil types at BBWM. The (NH4)2SO4 amendments in the treated watershed (West Bear) stimulated potential net nitrification, but significant increases were found only in hardwood O horizons after three years of treatment. Hardwood stand forest floor soil materials had the lowest C:N ratios (mean=23), compared with mixedwood (mean=27) and softwood stands (mean=33). NH4-N accounted for over 95% of the inorganic N in the forest floor. The lack of a strong relationship between soil type and potential net N mineralization at BBWM, coupled with conflicting results in the literature, suggested that stand characteristics were more important than conventional soil nomenclature based on pedogenetic features, or 2.5 years of treatments, in defining differences in soil N dynamics and responses to increased N inputs.     

Measurements of SO2, NO X and SPM in an industrial area at the Aegean coast of Turkey

Data from continuous measurements of SO₂ NO _x , suspended particulate matter (SPM) and meteorological parameters at seven sites around a highly industrialized region in the Aegean coast of Turkey, between July 15, 1991 to July 31, 1992 were used to evaluate spatial and temporal variations of air quality parameters. Low annual averages and insignificant differences between day and night concentrations were observed at stations far from sources. At stations close to sources, annual average concentrations were high and diurnal patterns were significant. Annual average SO₂ and SPM concentrations in all stations used the Krigging technique to assess the impact of industries on air quality in the surrounding airshed. Results have demonstrated that Turkish air quality standards for SO₂ were exceeded in a circle with a radius of 4 km and which was centered on the petrochemical complex and refinery. Similarly, standards for SPM were exceeded in a circle with a radius of 1.2 km and which was centered on the ironwork plants. Both SO₂ and SPM showed well defined diurnal variations, particularly in stations close to sources. The SO₂ concentrations showed a maximum during day-time, while SPM concentrations peaked after midnight. Although annual average SO₂ and SPM concentrations were highly variable depending on distances between stations and sources, background concentrations of the same pollutants, calculated by stripping episodes from data, did not change significantly from one station to another. Long range transport and resuspension of local soil were suggested as sources of background SO₂ and SPM, respectively. The difference between observed and background concentrations of SO₂ and SPM in each station was related to the impact of industries on air quality at that particular site.     

Mineral Soil and Solution Responses to Experimental N and S Enrichment at the Bear Brook Watershed in Maine (BBWM)

Buried mineral soil-bags and natural solutions were studied as indicators of forest ecosystem response to elevated N and S inputs at the Bear Brook Watershed in Maine (BBWM). The BBWM is the site of a paired watershed manipulation experiment in a northern New England forested ecosystem. The study includes two small (10 ha each) catchments dominated by northern hardwood forests with red spruce in the upper elevations. Treatments consist of (NH4)2SO4 applied to the West Bear watershed six times per year, increasing N and S deposition 3× and 2× above ambient values, respectively. Buried mineral soil-bag changes over time reflected both the native soil environment and the treatments. Most of the treatment effects on mineral soils were evident as higher inorganic S found in the treated watershed soils. Adsorbed SO4 in the buried mineral soil-bags increased by approximately 40% under softwood stands and 50% under hardwood stands over the study period. Hardwood soil solutions responded with significant increases in NO3 and SO4 concentrations that resulted in accelerated cation leaching, primarily Ca and Al. Few differences that could be attributed to treatments were evident in soil solutions under softwoods. No treatment effects were evident in throughfall and stemflow chemistry.     

Nitrogen and Sulfur Input-Output Budgets in the Experimental and Reference Watersheds, Bear Brook Watershed in Maine (BBWM)

Dry (NH4)2SO4 (1,800 eq-1 ha-1 yr-1) has been applied to the western of two contiguous 10 ha catchments at the Bear Brook Watershed in Maine (BBWM) since November, 1989. The initial rapid and significant response in both S and N in West Bear, compared to the reference East Bear, slowed after three years. Annual S retention of the total experimental treatment decreased from 86 to 34%, with a seven year cumulative retention of 59%. Hydrology influences the export flux of S; S is retained more in dry seasons and dry years. The annual retention of N has decreased from 96 to 81%, with a cumulative retention of 82%. The export of N from the reference watershed has declined from 178 to 23 eq-1 ha-1 yr-1 during the treatment period. The treatment N (as NH4) initially stimulated nitrification, and caused pre-existing N to be lost in runoff, rather than the treatment N. Retention of the treatment N has decreased to approximately 80%. The majority of the retained N is stored in the soil, but the reasons for the decreased flux from the reference watershed are not known.     

Influence of Meteorological Factors NO2, SO2, CO and PM10 on the Concentration of O3 in the Urban Atmosphere of Eastern Croatia

Ozone, NO₂, SO₂, CO, PM₁₀ and meteorological parameters were measured simultaneously during the summer?Cautumn season 2007 in Osijek??the eastern, flat, agricultural part of Croatia. Fourier analysis confirms the existence of variation in ozone volume fractions with periods ranging from the usual semi-daily and daily to 7 and 28 daily cycles. The relationships between O₃ and other variables were modelled in three ways: principal component analysis, multiple linear regression and principal component regression. The results of the principal component analysis detected underlying relationships among ozone concentrations and meteorological variables. An extremely simple meteorological model is suitable for the prediction of ozone levels. The meteorological factors, temperature and cloudiness played a main role in the MLR model (R ²?=?0.83). The application of the principal component regression approach confirmed that the original variables associated with the valid principal components were meteorological variables (R ²?=?0.82).     

Surfactant-mediated complex formation for determination of traces amounts of zinc, cadmium, and lead with 4-(2-thiazolylazo) resorcinol and chemometric methods

The partial least squares modeling is a powerful multivariate statistical tool applied to the spectrophotometric simultaneous determination of the divalent ions of zinc, cadmium, and lead based on the formation of their complexes with 4-(2-thiazolylazo) resorcinol in surfactant media. The linear concentration range for zinc, cadmium, and lead were 0.10-1.31, 0.148-1.92, and 0.148-3.70 mg L(?-1), respectively. The experimental calibration set was composed of 36 sample solutions using a mixture design for three component mixtures. The absorption spectra were recorded from 380 through 650 nm. The effect of pH on the sensitivity in determination of zinc, cadmium, and lead was studied in order to choose the optimum pH (pH = 8) for determination. The root-mean-square errors of predictions for zinc, cadmium, and lead were 0.0466, 0.0282, and 0.050, respectively. The proposed method was successfully applied for the determination of zinc, cadmium, and lead in water samples.