Heterogeneous Atmospheric Nitrogen Deposition Effects Upon the Nitrate Concentration of Stream Waters in a Forested Mountain Area

Nitrogen compounds generated by anthropogenic combustion deposits in forest watersheds and induce nitrogen saturation of the area. Because excess nitrogen is derived from atmospheric deposition, this action is expected to uniformly affect a wide area of forest soils. Geographically, heterogeneous nitrate concentration of stream water within a small area has been attributed to the tree type, geological setting and tree cut. In this article, we hypothesized that the effect of the atmospheric nitrogen deposition in the forest watershed may vary within a small area, and that such variation is induced by the degree of air mass containing a high concentration of nitrogen deposition of combustion origin. We measured major ion concentrations, including nitrate, nitrite oxygen and nitrogen stable isotope of nitrate sampled at 24 water streams in the Chichibu region, which is 50?C100 km from the Tokyo metropolitan area. The nitrate concentration showed a wide range (25.6?C237 ??mol L^?1) within 300 km², which was explained sufficiently by the air mass advection path and its contact with the mountain??s surface. The nitrate concentration showed a significant positive correlation with chloride (r?=?0.73; p?<?0.001). As chloride originates outside of the Chichibu region, the positive correlation between two ions showed that the nitrate concentration of the stream water was affected by the nitrogen compound from the Tokyo Metropolitan area as a form of atmospheric deposition. Between the nitrate concentration and the stable isotope ratio of oxygen of nitrate, there was a positive correlation until nitrate concentration of 100 ??mol L^?1. When the nitrate is over 100 ??mol L^?1, ??¹⁸O shows a stable value of ca. 5.7??. This indicates that the nitrification proceeds when the nitrate concentration was low to middle, but the reaction slowed when the nitrate concentration became high. Oxygen stable isotope of nitrate along with a set of nitrate concentrations can be used as a good indicator of nitrogen saturation.     

Characterization of nutrients uptake and enzymes activity in Khatouni melon (Cucumis melo var. inodorus) seedlings under different concentrations of nitrogen,potassium and phosphorus of nutrient solution

A nutrient solution experiment was done to evaluate effects of different concentrations of nitrogen (N), phosphorus (P) and potassium (K) on leaf mineral concentrations and some enzymes activity of melon seedlings (Cucumismelo var. inodorus subvar. Khatouni). Different levels of these nutrients including 0, 53, 105, 158 and 210?mg L^?1 N; 0, 8, 16, 23 and 31?mg L^?1 P; 0, 59, 118, 176 and 235?mg L^?1 K, all corresponding to 0, 25, 50, 75 and 100% of their concentrations in Hoagland nutrient solution, were applied to plants. The results showed that the highest leaf nitrate reductase (NR) activity was observed at highest N and P levels, whereas the three highest K levels showed the highest NR activity. The highest leaf peroxidase activity was observed at 8?mg L^?1 P, 59?mg L^?1 K and 158?mg L^?1 N. The leaf catalase activity was highest at zero concentration of P, 158?mg L^?1 N and 176?mg L^?1 K; however, catalase activity was decreased by increasing P levels. Leaf protein content showed an increasing trend with increasing N, P and K levels of nutrient solution, while there was no significant difference between 158 and 210?mg L^?1 N. The highest leaf concentrations of N, P, K and Mg were observed at highest nitrogen, potassium and phosphorus levels of nutrient solution, whereas the highest leaf concentration of Ca were obtained at 53 or 105?mg L^?1 N, 176?mg L^?1 K and 23–31?mg L^?1 P. The highest iron concentration of leaves was obtained from 23 to 31?mg L^?1 P, 176?mg L^?1 K and 210?mg L^?1 N.     

Toxicity of Synthetic Surfactants to the Marine Macroalga, Ulva lactuca

The toxicities of three synthetic surfactants to the marine macroalga, Ulva lactuca, have been examined by monitoring chlorophyll a fluorescence quenching. The anionic surfactant, sodium dodecyl sulphate (SDS), exerted no measurable toxicity over the concentration range 0?C10 mg L^?1, while presence of the non-ionic surfactant, Triton X-100 (TX), elicited a small reduction in photochemical efficiency that was independent of concentration. The cationic surfactant, hexadecyltrimethylammonium bromide (HDTMA), incurred a dose-dependent response to ??3 mg L^?1 (EC₅₀?=?2.4 mg L^?1), but a reduction in toxicity thereafter. Presence of TX had little effect on the toxicity of HDTMA but an equimolar concentration of SDS directly offset the impact of HDTMA on photochemical efficiency. Relative toxicities of the surfactants are attributed to differences in affinity for the algal surface and tendencies to disrupt cell membranes and interact with intracellular macromolecules. Non-linear dose responses and antagonistic effects are attributed to non-specific interactions between molecules of the same surfactant and electrostatic interactions between molecules of different amphiphilic character.     

Relationship Between pH and Stream Water Total Mercury Concentrations in Shenandoah National Park

The purpose of this study was to gather information on the spatial and temporal variation of stream water total mercury concentrations ([THg]) and to test the hypothesis that stream water [THg] increases as stream pH decreases in the Shenandoah National Park (SNP). We based our hypothesis on studies in lakes that found mercury methylation increases with decreasing pH, and studies in streams that found total mercury and other trace metal concentrations increase with decreasing pH. Stream water was collected at baseflow in SNP in April, July, and October 2005 and February 2006. Contrary to our hypothesis, stream water [THg] decreased with decreasing pH and acid neutralizing capacity. In SNP, stream pH and acid neutralizing capacity are strongly influenced by bedrock geology. We found that bedrock also influences stream water [THg]. Streams on basaltic bedrock had higher [THg] (0.648 ng L^?1?±?0.39) than streams on siliciclastic bedrock (0.301 ng L^?1?±?0.10) and streams on granitic bedrock (0.522 ng L^?1?±?0.06). The higher pH streams on basaltic bedrock had the highest [THg]. The variation in stream water [THg] occurred despite no known variation in wet deposition of mercury across the SNP. The findings of this study indicate that the SNP can be an important area for mercury research with significant variations in mercury concentrations across the park.     

Sediment denitrification in waterways in a rice-paddy-dominated watershed in eastern China

Purpose

Rice-paddy-dominated watersheds in eastern China are intensively cultivated, and lands with two crops receive as much as 550–600 kg?ha^–1?year^–1 of nitrogen (N), mainly through the addition of N-based fertilizers. However, stream N concentrations have been found to be relatively low. Waterways in the watersheds are assumed to be effective “sinks” for N, minimizing its downstream movement. We directly measured net sediment denitrification rates in three types of waterways (ponds, streams/rivers, and a reservoir) and determined the key factors that control net sediment denitrification. Such information is essential for evaluating the impact of the agricultural N cycle on the quality of surface water.

Materials and methods

The pond–stream–reservoir continuum was sampled every 2 months at nine sites in an agricultural watershed between November 2010 and December 2011. Net sediment N₂ fluxes/net sediment denitrification rates were determined by membrane inlet mass spectrometry and the N₂/Ar technique. A suite of parameters known to influence denitrification were also measured.

Results and discussion

Net denitrification rates ranged between 28.2?±?18.2 and 674.3?±?314.5 μmol N₂–N?m^–2?h^–1 for the streams, 23.7?±?23.9 and 121.2?±?38.7 μmol N₂–N?m^–2?h^–1 for the ponds, and 41.8?±?17.7 and 239.3?±?49.8 μmol N₂–N?m^–2?h^–1 for the reservoir. The mean net denitrification rate of the stream sites (173.2?±?248.4 μmol N₂–N?m^–2?h^–1) was significantly higher (p?<?0.001) than that of the pond sites (48.3?±?44.5 μmol N₂–N?m^–2?h^–1), and the three types of waterways all had significantly higher (p?<?0.01) mean net denitrification rates in summer than in other seasons. Linear regression and linear mixed effect model analysis showed that nitrate (NO₃ ^?–N) concentration in surface water was the primary controlling factor for net sediment denitrification, followed by water temperature. Using monitoring data on NO₃ ^?–N concentrations and temperature of the surface water of waterways and an established linear mixed effect model, total N removed through net sediment denitrification in the pond–stream–reservoir continuum was estimated at 46.8?±?24.0 t?year^–1 from July 2007 to June 2009, which was comparable with earlier estimates based on the mass balance method (34.3?±?12.7 t?year^–1), and accounted for 83.4 % of the total aquatic N. However, the total aquatic N was only 4.4 % of the total N input to the watershed, and thus most of the surplus N in the watershed was likely to be either denitrified or stored in soil.

Conclusions

High doses of N in a rice-paddy-dominated watershed did not lead to high stream N concentrations due to limited input of N into waterways and the high efficiency of waterways in removing N through denitrification.     

A Synoptic Survey of Nitrogen and Phosphorus in Tributary Streams and Great Rivers of the Upper Mississippi, Missouri, and Ohio River Basins

We combined stream chemistry and hydrology data from surveys of 436 tributary stream sites and 447 great river sites in the Upper Mississippi, Missouri and Ohio River basins to provide a regional snapshot of baseflow total nitrogen (TN) and total phosphorus (TP) concentrations, and to investigate the relationships between land use and stream chemistry. Catchments in the Upper Mississippi River basin had more land in agricultural uses (51%) than the Missouri or Ohio River basin catchments (25% and 29%, respectively). The difference in agriculture is reflected in the TN concentrations in tributary streams and the great rivers: 5,431 and 2,112 ??g L^?1 for the Upper Mississippi, 1,751 and 978 ??g L^?1 for the Missouri, and 1,074 and 1,152 ??g L^?1 for the Ohio River basins. This agricultural effect was not as evident for tributary stream or great river TP concentrations: 165 and 181 ??g L^?1 in the Upper Mississippi, 177 and 171 ??g L^?1 in the Missouri, and 67 and 53 ??g L^?1 in the Ohio River basins. We set reference thresholds based on the 75th percentile TN and TP concentrations at our least disturbed sites. The TN threshold was exceeded for 50?C63% of the tributary stream and 16?C55% of great river lengths, with the greatest proportion in the Upper Mississippi River basin. The TP threshold was exceeded in 32?C48% of tributary stream and 12?C41% of great river lengths. Tributary stream N/P ranged from 67:1 (Ohio) to 210:1 (Upper Mississippi); river N/P ranged from 20:1 (Missouri) to 60:1 (Ohio). N/P indicated that potential N-limitation occurred in 10?C21% of total tributary stream length and in 0?C46% of great river length; potential P-limitation ranged from 60?C83% of cumulative tributary stream length and from 21?C98% of cumulative great river length. Total N flux (concentration × discharge) was highest in the Upper Mississippi River basin; TP flux was lowest in the Ohio River basin. River TN yields and TP yields for both tributary streams and great rivers, was not significantly different between the sub-basins. Our study empirically links catchment land use and stream chemistry, and demonstrates using monitoring data for estimating nutrient yields at a large regional scale.     

Effects of Nitrogen Fertilization on Stream Chemistry of Japanese Forested Watersheds

Steam chemistry was investigated from May 1991 through April 1992 for 13 Japanese forested watersheds and from May 1990 through August 1994 for two of these watersheds. Nine watersheds were treated over different periods (1983–1991) with different amounts of N (nitrogen) fertilizer as urea and ammonium salts. Total N additions ranged from 20 to 375 kg ha^-1. There were no distinct seasonal differences in stream NO₃ ^- concentrations in either the treated or untreated watersheds, but concentrations tended to be somewhat higher during periods of high discharge. The annual average NO₃ ^- concentrations in streams had a significant, positive (p < 0.001, r = 0.84) relationship to the total amount of N applied from 1985–1991. The application of 330 kg N ha^-1 raised annual average stream NO₃ ^- concentration to about 300 μeq L^-1 compared to less than 160 μeq L^-1 in untreated watersheds. The concentrations of K⁺, Ca²⁺, and Mg2+ in stream water also increased in those watersheds with high rates of N fertilizer as a result of nitrification that increased the generation of the mobile nitrate anion. The lack of seasonality in stream NO₃ ^- concentrations and the large rates of N loss with N addition both suggest that these watersheds were ‘nitrogen saturated’     

Impact of land use on nitrogen concentration in groundwater and river water

Abstract

The aim of this study was to evaluate the impact of land use on nitrate nitrogen (NO₃-N) in shallow groundwater (G-N) and total nitrogen (N) in river water (R-N). The study area consisted of 26 watersheds (1342 km²) covering 72% of Kagawa Prefecture in Japan. We estimated G-N specific concentrations, which showed the magnitude of the upland fields, paddy fields, forests and urban land-use contributions to watershed-mean G-N. G-N specific concentrations were gained as partial regression coefficients using a multiple regression analysis of the watershed-mean G-N concentrations and the land-use ratios in each of the 26 watersheds. The results showed that the G-N specific concentration, which was gained as the partial regression coefficient for the multiple regression analysis, was 15.2 mg L^?1, 10.3 mg L^?1, 2.3 mg L^?1 and 2.5 mg L^?1 for the upland fields, paddy fields, forests and urban land-use types, respectively. R-N pollution load runoff to the river mouth was calculated by multiplying R-N specific concentration (previously reported) by river flow at the river mouth. Similarly, G-N pollution load arrival to groundwater was calculated by multiplying G-N specific concentration by the groundwater flow. The R-N pollution load runoff was 19.3 kg ha^?1 y^?1, 7.7 kg ha^?1 y^?1, 1.7 kg ha^?1 y^?1 and 7.6 kg ha^?1 y^?1, while the G-N pollution load arrival was 7.3 kg ha^?1 y^?1, 5.0 kg ha^?1 y^?1, 1.1 kg ha^?1 y^?1 and 1.2 kg ha^?1 y^?1, for upland fields, paddy fields, forests and urban areas, respectively. These results showed that the N in river water and groundwater was derived mainly from runoff and leaching from croplands. Therefore, the relationships between watershed-mean non-absorbed, applied nitrogen (NAA-N: nitrogen applied to cropland via fertilizer and manure without being absorbed by crops), R-N concentration and watershed-mean G-N concentration were investigated. A curvilinear correlation was observed between NAA-N and R-N concentrations (r² = 0.68) except for one small, high-density, urban watershed, and a weak linear correlation was observed between NAA-N and G-N concentrations (r² = 0.42).     

Integration of Soil pH with Soil‐Test Values of Zinc for Prediction of Yield Response in Rice Grown in Mollisols

Seventeen Mollisols having pH_(1:2) in the range of 6.00 to 8.42 were analyzed with five extractants, and the extractable zinc (Zn) ranges were 0.84 to 2.75 mg Zn kg^?1 soil for diethylenetriaminepentaacetic acid (DTPA) (pH 7.3), 0.91 to 2.72 mg Zn kg^?1 soil for DTPA + ammonium bicarbonate (pH 7.6), 1.82 to 7.18 mg Zn kg^?1 soil for Mehlich 3, 1.22 to 3.83 mg Zn kg^?1 soil for ethylenediaminetetraacetic acid (EDTA) + ammonium carbonate, and 0.88 to 1.18 mg Zn kg^?1 soil for 1 mol L^?1 magnesium chloride (MgCl₂) (pH 6.0). Zinc extracted by DTPA (pH 7.3) and Mehlich 3 showed significant positive correlation with sand content, whereas only Mehlich 3 showed negative correlation with soil pH. All extractants showed significant positive correlation with each other except for 1 mol L^?1 MgCl₂‐extractable Zn, which had significant positive correlation with only Mehlich 3– and EDTA + ammonium carbonate–extractable Zn. A greenhouse experiment showed that Bray's percentage yield of rice was poorly correlated to extractable soil Zn but had a significant and negative linear correlation with soil pH (r = ?0.662, significant at p = 0.01). Total Zn uptake by rice had a significant positive correlation with 1 mol L^?1 MgCl₂– and Mehlich 3–extractable Zn. A proposed parameter (p extractable Zn + p OH^?) involving both soil extractable Zn and pH terms together showed significant and positive correlation with Bray's percentage yield and total Zn uptake of rice. The calculated values of critical limits of soil Zn in terms of the proposed parameter were 14.1699 for DTPA (pH 7.3), 13.9587 for DTPA + ammonium bicarbonate, 13.7016 for Mehlich 3, 13.9402 for EDTA + ammonium carbonate, and 14.1810 for 1 mol L^?1 MgCl₂ (pH 6.0). The critical limits of Zn in rice grain and straw were 17.32 and 22.95 mg Zn kg^?1 plant tissue, respectively.     

Chemical characteristics and temporal trends in eight streams of the Catskill Mountains,New York

Discharge to concentration relationships for eight streams studied by the U.S. Geological Survey (USGS) as part of the U.S. Environmental Protection Agency's (U.S. EPA) Long-Term Monitoring Project (1983–89) indicate acidification of some streams by H₂SO₄ and HNO₃ in atmospheric deposition and by organic acids in soils. Concentrations of major ions in precipitation were similar to those reported at other sites in the northeastern United States. Average concentrations of SO₄ ^2? and NO₃ ^? were similar among streams, but base cation concentrations differed widely, and these differences paralleled the differences in acid neutralizing capacity (ANC). Baseflow ANC is not a reliable predictor of stream acidity at high flow; some streams with high baseflow ANC (>150 Μeq L^?1) declined to near zero ANC at high flow, and one stream with low baseflow ANC (<50 Μeq L^?1) did not approach zero ANC as flow increased. Episodic decreases in ANC and pH during peak flows were associated with increased concentrations of NO₃ ^? and dissolved organic carbon (DOC). Aluminum concentrations exceeding 300 Μg L^?1 were observed during peak flows in headwater streams of the Neversink River and Rondout Creek. Seasonal Kendall Tau tests for temporal trends indicate that SO₄ ^2? concentrations in streamwater generally decreased and NO₃ ^? concentrations increased during the period 1983–1989. Combined acid anion concentrations (SO₄ ^2? + NO₃ ^?) were generally unchanged throughout the period of record, indicating both that the status of these streams with respect to acidic deposition is unchanged, and that NO₃ ^? is gradually replacing SO₄ ^2? as the dominant acid anion in the Catskill streams.     

Nutrient dynamics of field-weathered Delmarva poultry litter: implications for land application

To develop phosphorus-based agronomic application rates of phytase-diet, bisulfate-amended Delmarva poultry litter in conservation tillage systems, nutrient release dynamics of the organic fertilizer under local weather conditions were investigated. Delmarva poultry litter was placed in polyvinyl chloride columns to a depth of 5 cm and weathered in the field for 570 days. Leachate from the columns was collected and measured for concentrations of various nutrients. Cumulative release of the nutrients as a function of weathering time was modeled, and the nutrient supply capacity was determined. Poultry litter leachate contained high contents of dissolved organic carbon (15–31,500 mg L^?1), nitrogen (N 5–7,070 mg L^?1), phosphorus (P 5–230 mg L^?1), potassium (K⁺ 2–7,140 mg L^?1), and other nutrients. Release of most nutrients occurred principally in the first 100 days, but for P and calcium (Ca²⁺), it would last for years. The release kinetics of N followed a logarithm equation, while P and K demonstrated a sigmoidal logistic pattern. The nutrient supply capacity of surface-applied Delmarva poultry litter was predicted at 10.9 kg N Mg^?1, 6.5 kg P Mg^?1, 34.7 kg K⁺ Mg^?1, 5.4 kg Ca²⁺ Mg^?1, and 14.0 kg SO ₄ ^2? Mg^?1. The results suggest that Delmarva poultry litter should be applied to conservation tillage systems at 6.6 Mg ha^?1 that would furnish 25 kg P ha^?1 and 63 kg N ha^?1 to seasonal crops. In repeated annual applications, the rate should be reduced to 5.2 Mg ha^?1, with supplemental N fertilization to meet crop N requirements.     

Behavior of Metals Under Different Seasonal Conditions: Effects on the Quality of a Mexico–USA Border River

Spatial and seasonal mobilization trends of metals in surface water were evaluated in the US–Mexico San Pedro River (SPR). Water samples were collected at five sampling stations for the analysis of dissolved oxygen, pH, electric conductivity, sulfates, and metals (Cd, Cu, Fe, Mn, Pb, and Zn). Quality of the water was characterized through Ecological Criteria of Water Quality (ECWQ) established in Mexico and Water Quality Criteria (Environmental Protection Agency (EPA)). High total metal concentrations were detected as follows: Fe?>?Cu?>?Mn?>?Zn?>?Pb?>?Cd. Metal concentrations were slightly higher in dry season than in rainy season: Cd (below detection limit (BDL)–0.21 mg L^?1), Cu (BDL–13 mg L^?1), Fe (0.16–345 mg L^?1), Mn (0.12–52 mg L^?1), Pb (BDL–0.48 mg L^?1), and Zn (0.03–17.8 mg L^?1). Low pH and dissolved oxygen values as well as high sulfate content were detected in both seasons. High values of metals (Cd, Cu, Fe, Mn, Pb, Zn) were detected at station E1 representing pollution source, as well as at stations E2 (Cd, Cu, Fe, Mn), E3 (Fe, Mn, Pb), and E4 and E5 (Fe, Mn). Detected concentrations exceeded maximum permissible established in ECWQ and Water Quality Criteria (EPA). Efflorescence salts on sediments in the dry season could increase levels of metals in water column. This study provides valuable information on the potential mobility of metals in surface water of SPR located in an arid environment where transport processes are strongly linked to climate. The information derived from this study should help the regional and national authorities to address present environmental regulations.     

Use of soil color meter for aqueous iron and ammonium measurements

Abstract

In this paper, we proposed a new approach for on-site colorimetric analysis of ferrous ions (Fe²⁺) and ammonium-nitrogen (NH₄ ⁺-N) using a soil color meter as an alternative method to conventional spectrophotometry. The soil color meter we used can express solution color numerically on the basis of L*a*b* color space. After coloring of water by the 1, 10 phenanthroline method and the Indophenol blue method, the color of solution was measured by the soil color meter. A linear relationship between Fe²⁺ and a* or b* values, and systematic change of NH₄ ⁺-N with L* value, enable us to make a calibration curve. The Fe²⁺ and NH₄ ⁺-N concentrations in groundwater samples (Fe²⁺: 0.3–1.3 mg L^?1; NH₄ ⁺-N: 0.02–0.62 mg L^?1) determined by the proposed method agreed well with those determined by conventional spectrophotometry with the difference being ± 0.05 mg L^?1 and ± 0.02 mg L^?1, respectively. Since a similar apparatus is widely used in the soil science field, this technique would facilitate field surveys.     

Optimum N and P rates for greenhouse production of vegetative coleus using constant liquid feed

Many new coleus (C. hybridus cv.) cultivars are vegetatively propagated and require different fertilization practices from seed propagated cultivars. Two experiments were conducted to evaluate growth responses of Henna, Indian Summer, Mint Mocha, New Orleans Red, Red Head, and Trusty Rusty to 0, 70, 140, 280 and 420 mg·L^?1 nitrogen (N), and Henna, Mint Mocha, Red Head, and Trusty Rusty to 0, 6.2, 12.4, 24.8, or 49.6 mg·L^?1 phosphorus (P) to determine optimum constant liquid feed rates to produce marketable size plants from rooted cuttings. Positive growth responses in terms of biomass were found with increasing N rates but not P rates. For medium-sized cultivars such as Henna, Indian Summer, and New Orleans Red, quadratic responses were found in aboveground biomass, and N at 280 mg·L^?1 resulted in similar plant size and dry weight as those fertilized at 140 and 420 mg·L^?1 N. For large-sized cultivars such as Mint Mocha, Red Head and Trusty Rusty, plant dry weight responded linearly within the N range tested and were greatest at 420 mg·L^?1. However, plant visual quality was negatively affected by N rates at 280 and 420 mg·L^?1 in that, leaf color became less intense at these high N rates. Plants fertilized at 70 mg·L^?1 were smaller than those fertilized at 140 mg·L^?1, however, they received similar visual quality ratings because of more intense leaf color. Therefore, N at 70 to 140 mg·L^?1 can be used to grow most vegetative coleus for similar marketable quality. Mint Mocha and Henna were the only cultivars responded to P treatments that, 12.4 mg·L^?1 P rate resulted in greater biomass than the no-P control. All other cultivars had no response to supplemental P except a linear response in tissue P%. Therefore, supplemental P is not required during the 8 week production period when there is an initial P charge in the substrate. We found that substrate pH decreases with higher P rates, therefore supplemental P fertilizer can be used for adjusting pH. Both N and P rates found optimum in this study are lower than current industry practices (N at 150 to 250 mg·L^?1 and P at 24 mg·L^?1) and can significantly lower production cost and potential leaching of excessive nutrient into waterway. Nutrient treatments in further study on postharvest performance of vegetative coleus will be selected based on this study.     

Occurrence of High In-Stream Nitrite Levels in a Temperate Region Agricultural Watershed

This study is the first to report nitrite occurrence and variability in surface water across an agricultural watershed in the province of Quebec, Canada. Nitrite (NO₂ ^?) concentrations were monitored across a 2.4 km² watershed during 2 years. Water samples were collected at the outlet from April to November and in three contrasted stream branches (six stations) during three hydrological regimes (summer low water levels, fall recharge, and snowmelt). Our study clearly demonstrates that NO₂ ^? levels observed at the outlet are not representative of NO₂ ^? variability across the micro-watershed. Surface water collected in cropped areas presents high NO₂ ^? concentrations during summer low water levels, often exceeding guidelines for aquatic life, with NO₂ ^? means ranging from 0.022 to 0.107 mg N L^?1 and maximum value reaching 0.156 mg N L^?1. Furthermore, the two stream branches in cropped area have demonstrated significant differences in NO₂ ^? concentrations and other water quality parameters. The importance of groundwater discharge to streams in the micro-watershed Bras d’Henri may potentially generate different in-stream sources of NO₂ ^? and water quality parameters. However, further studies are essential to determine sources and processes related to in-stream NO₂ ^? peaks.     

Versatile Flow Injection System for Spectrophotometric Determination of Silicon in Agronomic Samples

Abstract

A versatile flow injection system for spectrophotometric determination of silicon (Si) in agronomic samples is proposed. For plant and slag analysis (1.0–10.0 mg L^?1 Si), the method involves monitoring the yellowish molybdosilicic acid at 410 nm. Soil, fertilizer, water, and sugarcane juice analysis (0.5–5.0 mg L^?1 Si) were accomplished by adding a reducing agent, and the molybdenum blue compound that formed was monitored at 735 nm. Flexibility of the method allows determination in a variety of matrices involving a wide range of concentrations. Beer's law is followed up to 20.0 mg L^?1 Si (r<0.9997; n=6) for analysis at 410 nm and up to 10.0 mg L^?1 Si (r<0.9998; n=6) at 735 nm. For the yellow‐color and blue‐color methods, the detection limits were estimated as 0.5 and 0.1 mg L^?1 Si. Measurement frequency for both methods is approximately 75 h^?1 using 48 mg of ammonium heptamolybdate, 80 mg of oxalic acid, and 24 mg of ascorbic acid per determination. Results are precise (r.s.d.>0.1%, n=10) and in agreement with inductively coupled plasma–optical emission spectroscopy (ICP‐OES). Statistical differences between data sets were not confirmed after applying the Student's ttest at the 95% confidence level (t_exp=0.195>t_tab=2.57) related to n=6.     

Recent Atmospheric Deposition and its Effects on Sandstone Cliffs in Bohemian Switzerland National Park, Czech Republic

The protected area ??Bohemian Switzerland National Park?? with its characteristic sandstone landscape was influenced by the long-term air pollution and acidic deposition within the area known as Black Triangle (located where Germany, Poland, and the Czech Republic meet, is one of the Europe??s most polluted areas). The local Upper Cretaceous sandstone is subhorizontally stratified, fine- to coarse-grained, quartz dominated, with low content of clay minerals. One of the significant negative effects of the intensive acidic deposition on sandstone outcrops has been identified as chemical (salt) weathering, i.e., a process when the porous sandstone rock is except of chemical influence attacked also by force of crystallization of growing salts crystals. Anions NO ₃ ^? together with SO ₄ ^2? and cation NH ₄ ⁺ were the most abundant solutes in bulk precipitation samples. Current (2002 to 2009) bulk deposition fluxes of SO ₄ ^2? determined at three sites directly in the National Park indicate decline from 23 to 16 kg^?1 ha^?1 year^?1. Infiltration of bulk precipitation solutes into the sandstone mediates the weathering processes. Natural outflow of sandstone pore-water (sandstone percolates) can be sampled only during certain days of year when the sandstone becomes saturated with water and percolates drip out on small number of sites from roofs of overhangs. Under usual conditions percolation water evaporates at the sandstone surface producing salt efflorescences??the typical example is Prav?ická brána Arch locality. The average pH of the dripping sandstone percolates was 3.76. Concentration of SO ₄ ^2? and Al in sandstone percolates reached up to 46 and 10 mg L^?1. The concentration of Al in percolates has been 160-fold greater the one in the precipitation samples suggesting the sandstone as a source. The water O and H isotopic composition of percolates has been virtually identical to precipitation samples, indicating thus relatively short residence time of the solutions within the sandstone pore-spaces. Evaporation experiments with bulk precipitation and percolate samples proved possible origin of some Ca in bulk precipitation and the sandstone rock as the source of Al and possibly of K for the salt efflorescence identified on Rock Arch body.     

Geochemical Characteristics of Acidic Stream Water on Yakushima Island,a World Natural Heritage Site

We determined the chemical compositions of acidic stream waters on the rural, mountainous island of Yakushima (YK), and compared them with those of near-neutral stream waters in other mountainous watersheds in Japan. The pH and concentrations of the predominant sea-salt components (i.e., Cl^?, Na⁺, Mg²⁺) in YK water, particularly in streams with small watersheds, decrease with elevation, while the concentration of Al increases. In contrast, water in northwestern YK contains higher concentrations of non-sea-salt SO₄^2? and NO₃^? and of rock-derived cations such as Si and Ca²⁺ than water in eastern to southern YK. This clearly shows that the anthropogenic pollutants on YK are dominantly derived from the northwestern to western Asian continent rather than from Japan's main islands, which lie to the northeast. These pollutants are responsible for stream acidification on YK and for accelerating chemical weathering, mainly of plagioclase, in northwestern YK. Large amounts of acid rain on YK may enhance the formation of secondary minerals that strongly adsorb heavy metals, which can partly account for the low concentrations of heavy metals in YK waters.     

Automated Modification of the Molybdenum Blue Colorimetric Method for Phosphorus Determination in Soil Extracts

A flow injection analysis (FIA) method capable of automation for molybdate reactive phosphorus (P) determination in soil extracts is described. Results obtained using this method in three soil extracts [calcium chloride (CaCl₂), Olsen, and Mehlich I] were the same as those provided by the manual molybdate blue colorimetric method. Linear range extending to 2 mg P L^?1, detection limits ranging from 6 to 26 µg L^?1 depending on the soil extract, and accurate recoveries from P‐spiked samples were achieved. The sensitivity of the system was around 0.3 absorbance units per mg P L^?1, and the sampling frequency was 72 samples h^?1, higher than those described for most of the flow injection methods.     

Bioremoval of Surfactant from Laundry Wastewater in Optimized Condition by Anoxic Reactors

Effects of ethanol and nitrate on linear alkyl benzene sulfonate (LAS) degradation were investigated using central composite design. At experimental design, removal of 99.9% was observed in batch reactors (1 L) with 9.8 to 41.2 mg L^?1 of LAS. The batch reactors were kept under agitation at 120 rpm and 30 °C. Ethanol (co-substrate) and nitrate (electron acceptor) were statistically significant factors (p?<?0.05) in surfactant removal. Optimal values were 97.5 and 88 mg L^?1 for ethanol and nitrate, respectively. LAS removal was kinetically investigated by varying surfactant concentration while using optimal values. Batch I (27 mg L^?1 LAS) exhibited greater degradation rate (K^LAS) (0.054 h^?1) in the presence of ethanol and nitrate. Nonetheless, in Batch II (60 mg L^?1 LAS), the K^LAS values decreased in those reactors probably due to inhibition by excess substrate for same concentrations of nitrate and ethanol added in reactors. As LAS concentration increased, the dominance of bacterial populations also increased, whereas diversity index decreased from 2.8 (inoculum) to 2.4 and 2.5 for reactors with both added nitrate and ethanol and those with only added ethanol, respectively. Probably, a selection of microbial populations occurred in relation to LAS concentration. The nitrate and ethanol, at able concentration, made it possible the induction of denitrifying microrganisms foward to LAS removal.