Fluoride occurrence and assessment of exposure dose of fluoride in shallow aquifers of Makur, Unnao district Uttar Pradesh, India

The water samples from the shallow aquifers of Makur, Unnao district, Uttar Pradesh, was analyzed for fluoride content (F( - )) and other water quality parameters such as pH, EC, CO(3) (2-), HCO(3) (-), Cl( - ), Na( + ), Ca(2 + ), Mg(2 + ) and RSC. It was found that the F( - ) concentration of water varied between 1.05 to 13.9 mgl( - 1) which exceeded the maximum desirable limits of 1.0 mgl( - 1) of F( - ) as laid down by BIS and 68% of water exceeded maximum permissible limits of 1.5 mgl( - 1) as prescribed by WHO. The correlation study of fluoride indicated that F( - ) has a significant (p < 0.05) positive relationship with pH (r = +0.59) and RSC (r = 0.54), while a significant negative correlation with Ca+Mg (r = -0.53) and Mg (r = -0.49). The exposure doses of fluoride in infants was found between 0.35 to 3.26 mg kg( - 1)day( - 1) (if dug well water was used) whereas 0.36 to 4.63 mg kg( - 1)day( - 1) (when shallow hand pumps) The exposure doses of water in case of children (20 kg body weight) varied between 0.157 to 1.47 mg kg( - 1)day( - 1) (for dugwell) and 0.162 to 2.08 mg kg( - 1)day( - 1) (for shallow hand pumps) whereas in case of adults (70 kg body weight), it varied between 0.09 to 0.839 mg kg( - 1)day( - 1) (for dugwell) and 0.092 to 1.19 mg kg( - 1)day( - 1) (shallow hand pumps) which is quite high against the standard value of 0.05 mg/kg/day which is the minimum risk level (MRL) calculated by the Agency for Toxic Substances and Disease Registry (ATSDR). The maximum exposure dose to fluoride for adults in the study area found to be 23.8 times higher than the ATSDR's MRL.     

Pollution and variation of stream nitrate in a protected high-mountain watershed of Central Taiwan: evidence from nitrate concentration and nitrogen and oxygen isotope compositions

This study analyzed the concentration and stable nitrogen (δ(15)N) and oxygen (δ(18)O) isotopic compositions of water NO (3) (-) , as well as NO (3) (-) concentration and δ(15)N values of soils and manure-sourced fertilizers to assess pollution and variation in stream nitrate at the watershed of the Chi-Chia-Wan Stream (CCWS), a protected high-mountain stream in Central Taiwan. Results indicate a gully (G1) that contributes significantly high NO (3) (-) concentration water (up to 122 mg/L) to trunk water as the major pollution source of CCWS. The high NO (3) (-) concentration gully water has a close relationship with manure-sourced fertilizer with both having compatible enriched δ(15)N values. Results also indicate that water mixing over isotopic fractionation processes such as denitrification or assimilation is the major process accounting for variations in concentrations and isotopic values for stream NO (3) (-) . Incorporation of gully/tributary water of high NO (3) (-) concentration increases both the concentration and isotopic values of trunk water and vice versa for the incorporation of low NO (3) (-) concentration tributary water. Despite G1 contributing high NO (3) (-) concentration water to the trunk water of CCWS, the concentration of the trunk water is only slightly elevated and is still lower than the required water quality standard due to much lower drainage of the gully water compared to trunk water's runoff. In addition to gully or tributary water and rainwater, NO (3) (-) derived from soil is another important contributor to trunk water. The NO (3) (-) contribution of soil to trunk water is greater in summer than in winter. Additionally, NO (3) (-) concentrations in soil from ex-cultivated land are significantly lower than that in cultivated land. This means that NO (3) (-) contribution from ex-cultivated land soil to trunk water is small and demonstrates that the land-recovery plan that has been underway in the studied watershed for sometime is effective.     

Enantioselective ecotoxicity of the herbicide dichlorprop and complexes formed with chitosan in two fresh water green algae

To reduce the leaching potential, to prevent groundwater contamination and to maintain the efficacy of a pesticide, natural polysaccharides have received increasing attention due to their biocompatibility and useful biological reactivity for controlled release formulations (CRFs) of pesticides. In this paper, the toxicities of the chiral herbicide dichlorprop (DCPP) and its complexes with chitosan molecules (DCPP-CS) and chitosan nanoparticles (DCPP-NP) to two different green algae were determined and compared. The inhibition rates of DCPP, DCPP-CS and DCPP-NP were determined at 24, 48, 72, 96, 120, 144, 168 h, and the results show that (S)-DCPP was more toxic to Chlorella vulgaris than (R)-DCPP, while the (R)-DCPP was more toxic to Scenedesmus obliquus than (S)-DCPP. The study also found that the chiral selectivity of DCPP to Chlorella vulgaris and Scenedesmus obliquus could be changed when DCPP was complexed with chitosan molecules (CS) or chitosan nanoparticles (NP). For Chlorella vulgaris, the order of inhibition was (R)-DCPP-CS > (S)-DCPP-CS and (R)-DCPP-NP > (S)-DCPP-NP; for Scenedesmus obliquus, the order was (S)-DCPP-CS > (R)-DCPP-CS and (S)-DCPP-NP > (R)-DCPP-NP. This phenomenon suggests that the enantioselective behaviors of chiral compounds might shift when interactions with other chiral receptors coexist in different biological environments. Additionally, chitosan molecules and chitosan nanoparticles also showed different toxicities, which could be ascribed to the difference in the physicochemical properties between CS and NP or the differences in the cell walls of the two fresh water green algae.     

Development of an integrated sensor to measure odors

Odorous air samples collected from several sources were presented to an olfactometer, an electronic nose, a hydrogen sulfide (H(2)S) detector and an ammonia (NH(3)) detector. The olfactometry measurements were used as the expected values while measurements from the other instrumentation values became input variables. Five hypotheses were established to relate the input variables and the expected values. Both linear regression and artificial neural network analyses were used to test the hypotheses. Principal component analysis was utilized to reduce the dimensionality of the electronic nose measurements from 33 to 3 without significant loss of information. The electronic nose or the H(2)S detector can individually predict odor concentration measurements with similar accuracy (R (2) = 0.46 and 0.50, respectively). Although the NH(3) detector alone has a very poor relationship with odor concentration measurements, combining the H(2)S and NH(3) detectors can predict odor concentrations more accurately (R (2) = 0.58) than either individual instrument. Data from the integration of the electronic nose, H(2)S, and NH(3) detectors produce the best prediction of odor concentrations (R (2) = 0.75). With this accuracy, odor concentration measurements can be confidently represented by integrating an electronic nose, and H(2)S and NH(3) detectors.     

Oxidation of Cr(III) to Cr(VI) during chlorination of drinking water

Drinking water treatment typically uses strong oxidants such as chlorine which are capable of converting Cr(III) to Cr(VI). The rates and extent of Cr(III) oxidation by chlorine are not well established. Cr(III) oxidation experiments were therefore conducted in distilled deionized water and New York City tap water dosed initially with Cr(III) and supplemented with sodium hypochlorite to increase free chlorine residual. Reaction progress was monitored using capillary electrophoresis which quenched reactions and allowed for quantification of Cr(VI). Three different forms of Cr(III) were used as reactants: a Cr(III) nitrate salt, Cr(III)-EDTA, and Cr(III) hydroxide. Rates of Cr(VI) production for all three forms of Cr(III) were rapid, on the order of hours. However, oxidation rates slowed and a plateau in Cr(VI) concentrations was reached. This resulted in less than 100% conversion of Cr(III) to Cr(VI) even at relatively high chlorine doses (10 to 100 mg L(-1) as Cl(2)). The loss of free chlorine due to a non-Cr chlorine demand, the precipitation of Cr(III) to Cr(OH)(3)(s), and the partial oxidation of Cr(III) to intermediate oxidation states (i.e. Cr(IV) and Cr(V)) were examined and eliminated as possible explanations for this behavior. Consumption of chlorine via reaction with intermediate oxidation states of Cr is therefore offered as a possible explanation for the plateau in Cr(VI) concentrations.     

Plants as bio-monitors for Cs-137, Pu-238, Pu-239,240 and K-40 at the Savannah River Site

The Savannah River Site was constructed in South Carolina to produce plutonium (Pu) in the 1950s. Discharges associated with these now-ceased operations have contaminated large areas within the site, particularly streams associated with reactor cooling basins. Evaluating the exposure risk of contamination to an ecosystem requires methodologies that can assess the bioavailability of contaminants. Plants, as primary producers, represent an important mode of transfer of contaminants from soils and sediments into the food chain. The objective of this study was to identify local area plants for their ability to act as bio-monitors of radionuclides. The concentrations of cesium-137 ((137)Cs), potassium-40 ((40)K), (238)Pu and (239,240)Pu in plants and their associated soils were determined using γ and α spectrometry. The ratio of contamination concentration found in the plant relative to the soil was calculated to assess a concentration ratio (CR). The highest CR for (137)Cs was found in Pinus palustris needles (CR of 2.18). The correlation of soil and plant (137)Cs concentration was strong (0.76) and the R(2) (0.58) from the regression was significant (p = 0.006). This suggests the ability to predict the degree of (137)Cs contamination of a soil through analysis of the pine needles. The (238)Pu and (239,240)Pu concentrations were most elevated within the plant roots. Extremely high CR values were found in Sparganium americanum (bur-reed) roots with a value of 5.86 for (238)Pu and 5.66 for (239,240)Pu. The concentration of (40)K was measured as a known congener of (137)C. Comparing (40)K and (137)C concentrations in each plant revealed an inverse relationship for these radioisotopes. Correlating (40)K and (137)Cs was most effective in identifying plants that have a high affinity for (137)Cs uptake. The P. palustris and S. americanum proved to be particularly strong accumulators of all K congeners from the soil. Some species that were measured, warrant further investigation, are the carnivorous plant Utricularia inflata (bladderwort) and the emergent macrophyte Juncus effusus. For U. inflata, the levels of (137)Cs, (238)Pu, and (239,240)Pu (which were 3922, 8399, and 803 Bq kg(-1), respectively) in the leaves were extremely high. The highest (137)Cs concentration from the study was measured in the J. effusus root (5721 Bq kg(-1)).     

Long-term investigations of post-Chernobyl radiocaesium in fallout and air in North Croatia

The long-term behaviour of (137)Cs activity concentrations in air and fallout has been studied in the city of Zagreb for the post-Chernobyl period (1986-2006) as a part of an extended monitoring program of radioactive contamination of human environment in Croatia. Annual mean (137)Cs activity concentrations in air and annual total deposition fluxes (wet plus dry) decreased from 2.8 x 10(-4) Bq m(-3) in September 1986 to 3.0 x 10(-6) Bq m(-3) in last quarter of 2006 and from 6,410 Bq m(-2) year(-1) in 1986 to 2 Bq m(-2) year(-1) in 2006 respectively. By fitting the measured (137)Cs activity concentrations to the theoretical curve the ecological half-lives of (137)Cs in air and fallout were estimated with respective values of 0.46 and 0.54 years for immediate post-Chernobyl period, increasing to 5.52 and 3.97 years afterwards. Using the data on (137)Cs activity concentrations in air and fallout total caesium deposition velocity of (3.34 +/- 3.13) x 10(-2) ms(-1) was estimated with median value being 2.13 x 10(-2) ms(-1). Such relatively high (137)Cs deposition velocities compared with pre-Chernobyl ones, are characteristic for the post-Chernobyl period and, according to Stokes' settling law, indicate that the diameters of aerosol particles associated with (137)Cs originated from the Chernobyl accident are pretty large, i.e. >1 microm. (134)Cs/(137)Cs activity ratio in fallout and in air has been found to be similar to the theoretically predicted values, initial value being about 0.5 and decreasing according to differential radioactive decay. The similar ratio has been observed in most of the other environmental samples.     

Relationship between CH₄ and N₂O flux from soil and their ambient mixing ratio in a riparian rice-based agroecosystem of tropical region

Temporal variations of the ambient mixing ratio of greenhouse gas (CH(4) and N(2)O) in a riparian rice-based agro-ecosystem of tropical region were studied during 2005-2006 in coastal Odisha. The endeavour was made with the hypothesis that the ambient mixing ratio of CH(4) and N(2)O depends on the changes in the flux of CH(4) and N(2)O from the rice fields in the riparian rice ecosystems. A higher ambient mixing ratio of CH(4) was recorded during the tillering to grain filling stages of the rice crop, during both dry and wet seasons. The higher ambient mixing ratio of CH(4) during the wet season may attribute to the higher CH(4) emission from the rice field. The average mixing ratio of CH(4) was recorded as 1.84 ± 0.05 ppmv and 1.85 ± 0.06 ppmv during 2005 and 2006, respectively. The ambient CH(4) mixing ratio was recorded negatively correlated with the average ambient temperature. The N(2)O mixing ratio ranged from 261.57 to 399.44 ppbv with an average of 330.57 ppbv during 2005. However, the average mixing ratio of N(2)O was recorded as 318.83 ± 20.00 ppbv during 2006. The N(2)O mixing ratio was recorded to be negatively correlated with rainfall and average ambient temperature. Significant negative correlation (r = -0.209) of N(2)O with sunshine hours may attribute to the photochemical break down of N(2)O. The temporal variation of N(2)O flux from the rice field does not affect the ambient mixing ratio of N(2)O in the same way as in the case of the ambient mixing ratio of CH(4). However, the higher mixing ratio of N(2)O during the fallow period of the post monsoon period may attribute to the N(2)O flux from soil. Results indicate that intensively cultivated coastal ecosystems can be a major source of ambient greenhouse gas.     

Atmospheric wet deposition of soluble macro-nutrients in the Cilician Basin, north-eastern Mediterranean sea

In order to estimate wet deposition atmospheric fluxes of macro-nutrients into the eastern Mediterranean coastal waters, soluble inorganic phosphate (PO4(3-)), nitrate (NO3-) and nitrite (NO2-) concentrations in precipitation (from February 1996 to June 1997) have been measured at a coastal sampling site, Erdemli, Turkey. Water-soluble inorganic PO4(3)-P, a reactive, bioavailable, limiting macro-nutrient in the oligotrophic waters of the eastern Mediterranean was studied with respect to its contribution to biological productivity. Reactive PO4(3-)-P and NO2(-) + NO3(-)-N concentrations were found to be highly variable in rainwater samples. One of the aims of the study was to determine the contribution of dust transport to the soluble macro-nutrient budget of the eastern Mediterranean. No differences were found between the mean reactive P and NO(2-) + NO3(-)-N concentrations of "red rain" and normal rain events. Most likely as a result of low solubility of crustal phosphorus, dust episodes were not found to be important sources of reactive P, in terms of wet deposition. The annual wet deposition fluxes of reactive PO4(3-)-P and NO2(-) + NO3(-)-N into the Cilician Basin were respectively estimated to be 0.010 g P m(-2) per year and 0.23 g N m(-2) per year, which are comparable to the fluxes from land-based sources in the north-eastern Mediterranean. The incorporation of water soluble bioavailable PO4(3-)-P and NO2(-) + NO3(-)-N delivered via atmospheric wet deposition could be responsible for approximately 3.3% (0.40 g C m(-2) per year) and 11.0% (1.31 g C m(-2) per year) respectively, of the mean annual new production in the north-eastern Mediterranean.     

Comparison of the SidePak personal monitor with the Aerosol Particle Sizer (APS)

The aim of this study was to compare the performance of the TSI Aerodynamic Particle Sizer (APS) and the TSI portable photometer SidePak to measure airborne oil mist particulate matter (PM) with aerodynamic diameters below 10 μm, 2.5 μm and 1 μm (PM(10), PM(2.5) and PM(1)). Three SidePaks each fitted with either a PM(10), PM(2.5) or a PM(1) impactor and an APS were run side by side in a controlled chamber. Oil mist from two different mineral oils and two different drilling fluid systems commonly used in offshore drilling technologies were generated using a nebulizer. Compared to the APS, the SidePaks overestimated the concentration of PM(10) and PM(2.5) by one order of magnitude and PM(1) concentrations by two orders of magnitude after exposure to oil mist for 3.3-6.5 min at concentrations ranging from 0.003 to 18.1 mg m(-3) for PM(10), 0.002 to 3.96 mg m(-3) for PM(2.5) and 0.001 to 0.418 mg m(-3) for PM(1) (as measured by the APS). In a second experiment a SidePak monitor previously exposed to oil mist overestimated PM(10) concentrations by 27% compared to measurements from another SidePak never exposed to oil mist. This could be a result of condensation of oil mist droplets in the optical system of the SidePak. The SidePak is a very useful instrument for personal monitoring in occupational hygiene due to its light weight and quiet pump. However, it may not be suitable for the measurement of particle concentrations from oil mist.     

Insights into ozone deposition patterns from decade-long ozone flux measurements over a mixed temperate forest

Long-term fluxes of ozone (O(3)) were measured over a mixed temperate forest using the aerodynamic gradient method. The long-term average O(3) flux (F) was -366 ng m(-2) s(-1) for the period 2000-2010, corresponding to an average O(3) concentration of 48 μg m(-3) and a deposition velocity v(d) of 9 mm s(-1). Average nocturnal ozone deposition amounted to -190 ng m(-2) s(-1), which was about one third of the daytime flux. Also during the winter period substantial O(3) deposition was measured. In addition, total O(3) fluxes were found to differ significantly among canopy wetness categories. During the day, highest deposition fluxes were generally measured for a dry canopy, whereas a rain-wetted canopy constituted the best sink at night. Flux partitioning calculations revealed that the stomatal flux (F(s)) contributed 20% to the total F but the F(s)/F fraction was subject to seasonal and diurnal changes. The annual concentration-based index AOT40 (accumulated dose over a threshold of 40 ppb) and the Phytotoxic Ozone Dose (POD(1) or accumulated stomatal flux above a threshold of 1 nmol m(-2) s(-1)) were related in a curvilinear way. The O(3) deposition was found to be largely controlled by non-stomatal sinks, whose strength was enhanced by high friction velocities (u(*)), optimizing the mechanical mixing of O(3) into the canopy and the trunk space. The long-term geometrical mean of the non-stomatal resistance (R(ns)) was 136 s m(-1) but lower R(ns) values were encountered during the winter half-year due to higher u(*). The R(ns) was also subject to a marked diurnal variability, with low R(ns) in the morning hours, when turbulence took off. We speculate that non-stomatal deposition was largely driven by scavenging of ozone by biogenic volatile organic compounds (BVOCs) and especially NO emitted from the crown or the forest floor.     

Occurrence and fate of androgens, estrogens, glucocorticoids and progestagens in two different types of municipal wastewater treatment plants

The occurrence and fate of fourteen androgens, four estrogens, five glucocorticoids and five progestagens were investigated in two different types of wastewater treatment plants (Plant A: activated sludge with chlorination, and Plant B: oxidation ditch with UV) of Guangdong province, China. 14, 14, and 10 of 28 target compounds were detected in the influent, effluent and dewatered sludge samples with the concentrations ranging from below 1.2 ± 0.0 ng L(-1) (stanozolol) to 1368 ± 283 ng L(-1) (epi-androsterone), below 1.0 ± 0.0 ng L(-1) (progesterone) to 23.1 ± 1.0 ng L(-1) (5α-dihydrotestosterone), 1.0 ± 0.1 ng g(-1) (estrone) to 460 ± 4.4 ng g(-1) (5α-dihydrotestosterone), respectively. The concentrations of total androgens (1554-1778 ng L(-1) in influent, 13.3-47.8 ng L(-1) in effluent, 377-923 ng g(-1) in dewatered sludge) were much higher than those of total estrogens (41.5-60.2 ng L(-1) in influent, 5.6-13.5 ng L(-1) in effluent, 13.9-57.8 ng g(-1) in dewatered sludge), glucocorticoids (171-192 ng L(-1) in influent, 2.2-6.3 ng L(-1) in effluent, N.D.-4.4 ng g(-1) in dewatered sludge), and progestagens (39.6-40.5 ng L(-1) in influent, 6.9-12.1 ng L(-1) in effluent, N.D. in dewatered sludge) in these two WWTPs. According to mass balance analysis, the removal rates of most target steroids in Plant A had exceeded 90%, while those in Plant B for nearly half of detected target steroids were lower than 80%. It is obvious that the treatment capacity of the activated sludge system (Plant A) is superior to the oxidation ditch (Plant B) in the degradation of steroids in sewage treatment systems. Androgens, estrogens and progestagens were mainly removed by sorption and degradation, while the reduction of glucocorticoids was primarily due to degradation.     

Determination of organophosphorus fire retardants and plasticizers in wastewater samples using MAE-SPME with GC-ICPMS and GC-TOFMS detection

Determination of organophosphorus fire retardants and plasticizers at trace levels in wastewater is described. In this work, microwave assisted extraction (MAE) and solid-phase microextraction (SPME) are used for sample preparation to extract and preconcentrate the analytes, followed by analysis by gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) for phosphorus-specific detection. Gas chromatography coupled to time of flight mass spectrometry (GC-TOF-MS) was used to confirm the organphosphorus fire retardants in wastewater. The detection limits of organophosphorus fire retardants (OPFRs) were 29 ng L(-1) for tri-n-butyl phosphate (TnBP), 45 ng for L(-1) for tris(2-butoxyethyl)phosphate (TBEP), and 50 ng L(-1) for tris(2-ethylhexyl)phosphate (TEHP). Optimized extraction conditions were performed at 65 degrees C for 30 min and with 10% NaCl. Application of MAE during the sample preparation prior to the SPME allowed the detection of tris(2-ethylhexyl) phosphate, which has been difficult to determine in previous work. Application of the method to wastewater samples resulted in detecting 3.1 microg L(-1) P from TnBP, 5.0 microg L(-1) P from TBEP, and 4.0 microg L(-1) P from TEHP. The presence of these compounds were also confirmed by SPME-GC-TOF-MS.     

Enantiomer ratios,patterns and levels of toxaphene congeners in human milk from Germany

High resolution gas chromatography (HRGC) coupled to quadrupole negative ion chemical ionization (NICI) mass spectrometry (MS) was used to investigate congener patterns, levels and enantiomer distribution of selected toxaphene congeners (#26, #41, #44, #50, #63, B7-1453) in human milk from Germany. #50 and #26 were the most abundant congeners. Furthermore, the identification of B7-1453, B8-1412, #41, #42, #44 and #63 was possible. Levels for the sum of #26, #41, #44 and #50 ranged from 7 to 24 microg kg(-1) milk fat and contributed between 2 and 9% to the total burden of investigated organochlorines such as selected compounds of the chlordane group, HCH, DDT and polychlorinated biphenyls (PCB). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Enantiomer ratios (ER) and enantiomer fractions (EF) of the abundant toxaphene congeners #26 and #50 as well as of B7-1453, #41 and #63 were determined. Greatest deviations from a racemic composition in individual human milk samples were found for #41 (1.54-2.37), #50 (1.37-1.72) and #63 (0.53-0.71) whereas ERs for #26 were close to 1. Compared to wildlife biota such as fish and raptors ER changes were more pronounced in human milk but comparable to human adipose tissue.     

Assessing impact of industrialization in terms of LULC in a dry tropical region (Chhattisgarh), India using remote sensing data and GIS over a period of 30 years

The main focus of the paper is to assess the land use/ land cover (LULC) change in northern Chhattisgarh due to industrialization using remote sensing and Geographical Information System (GIS). The impact was assessed using an information extraction method applied to temporal satellite data (LANDSAT and IRS scenes) in GIS domain. For assessing the impact on natural resources, the classification scheme was restricted to (1) Forest patches ((a) completely cleared, (b) partially cleared, (c) least affected), (2) Non-Forest ((d) completely changed, (e) least changed), (3) Industrial/Mining area, and (4) River. Over the three decades 22.22% of forests have been completely cleared and converted to industrial setup. Another 25% is completely cleared and 10% is degraded. Around 4% of agricultural area is totally affected due to industrial activity. Random assessment of plant distribution (Trees, Shrubs and Herbs) indicates significant changes in the herb distribution directly related to distance gradient form the industrial/mining setup. Visual recording, socio-economic survey and satellite data also helped in delineation of extent of environmental pollution in forest and non-forest areas. The paper presents methodology for the environmental impact assessment.     

Matrix-bound phosphine and phosphorus fractions in paddy soils

Phosphine (PH(3)) is a natural gaseous carrier of phosphorus (P) in its geochemical cycles, and it might be important to the P balance of natural ecosystems. Paddy fields are thought to be one of the main sources responsible for the production and emission of PH(3) in to the environment. The relationships between matrix-bound PH(3) (MBP) and different P fractions, as well as selected metals were investigated to explore the possible production of MBP and its link to P cycle in the paddy soils. MBP range from 20.8 (-1) to 502 ng kg(-1) with an average of 145 ng kg(-1). Concentrations at the milk stage are significantly higher than at the jointing stage. The total P range from 333 mg kg(-1) to 592 mg kg(-1). Average P fractions decrease in the order: Ca-P (69.9%) > Organic P (16.5%) > occluded P (6.50%) > Fe-P (5.93%) > dissolved P (0.80%) > exchangeable P (0.32%) > Al-P (0.02%). Different levels of nitrogen fertilizer have little effect on the contents of MBP, P fractions and metals. A significant positive correlation between MBP and Ca-P (p = 0.002), as well as between MBP and Ca (p = 0.008) could be observed, suggesting that Ca-P mainly affects the production of MBP in the paddy soils. It is suggested that soil MBP is strongly linked to Ca-P fertilizer use because soil spiked with P-fertilizer produced an additional 758 ± 142 ng of MBP per kg of soil, compared to only 81.7 ± 12.3 ng of MBP per kg of unspiked soil. No correlations are found between MBP and other P fractions, or between MBP and Al, Fe and Mn.     

Satellite detection of land-use change and effects on regional forest aboveground biomass estimates

We used remote-sensing-driven models to detect land-cover change effects on forest aboveground biomass (AGB) density (Mg.ha(-1), dry weight) and total AGB (Tg) in Minnesota, Wisconsin, and Michigan USA, between the years 1992-2001, and conducted an evaluation of the approach. Inputs included remotely-sensed 1992 reflectance data and land-cover map (University of Maryland) from Advanced Very High Resolution Radiometer (AVHRR) and 2001 products from Moderate Resolution Imaging Spectroradiometer (MODIS) at 1-km resolution for the region; and 30-m resolution land-cover maps from the National Land Cover Data (NLCD) for a subarea to conduct nine simulations to address our questions. Sensitivity analysis showed that (1) AVHRR data tended to underestimate AGB density by 11%, on average, compared to that estimated using MODIS data; (2) regional mean AGB density increased slightly from 124 (1992) to 126 Mg ha(-1) (2001) by 1.6%; (3) a substantial decrease in total forest AGB across the region was detected, from 2,507 (1992) to 1,961 Tg (2001), an annual rate of -2.4%; and (4) in the subarea, while NLCD-based estimates suggested a 26% decrease in total AGB from 1992 to 2001, AVHRR/MODIS-based estimates indicated a 36% increase. The major source of uncertainty in change detection of total forest AGB over large areas was due to area differences from using land-cover maps produced by different sources. Scaling up 30-m land-cover map to 1-km resolution caused a mean difference of 8% (in absolute value) in forest area estimates at the county-level ranging from 0 to 17% within a 95% confidence interval.     

Simultaneous determination of atmospheric sulfur and nitrogen oxides using a battery-operated portable filter pack sampler

We developed a method to analyze atmospheric SO(x) (particulate SO(4)(2-)+ gaseous SO(2)) and NO(x) (NO + NO(2)) simultaneously using a battery-operated portable filter pack sampler. NO(x) determination using a filter pack method is new. SO(x) and NO(x) were collected on a Na(2)CO(3) filter and PTIO (2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl) + TEA (triethanolamine) filters (6 piled sheets), respectively. Aqueous solutions were then used to extract pollutants trapped by the filters and the resulting extracts were pre-cleaned (e.g. elimination of PTIO) and analyzed for sulfate and nitrite by ion chromatography. Recoveries of SO(2) and NO(x) from standard pollutant gases and consistency of the field data with those from other instrumental methods were examined to evaluate our method. SO(x) and NO(x) could be analyzed accurately with determination limits of 0.2 ppbv and 1.0 ppbv (as daily average concentrations), respectively. The sampler can determine SO(x) and NO(x) concentrations at mountainous or remote sites without needing an electric power supply.     

Acute O 3 damage on first year coppice sprouts of aspen and maple sprouts in an open-air experiment

We studied the effect of high ozone (O(3)) concentration (110-490 nmol mol(-1)) on regenerating aspen (Populus tremuloides) and maple (Acer saccharum) trees at an open-air O(3) pollution experiment near Rhinelander WI USA. This study is the first of its kind to examine the effects of acute O(3) exposure on aspen and maple sprouts after the parent trees, which were grown under elevated O(3) and/or CO(2) for 12 years, were harvested. Acute O(3) damage was not uniform within the crowns of aspen suckers; it was most severe in the mature, fully expanded photosynthesizing leaves. Young expanding leaves showed no visible signs of acute O(3) damage contrary to expectations. Stomatal conductance played a primary role in the severity of acute O(3) damage as it directly controlled O(3) uptake. Maple sprouts, which had lower stomatal conductance, smaller stomatal aperture, higher stomatal density and larger leaf surface area, were tolerant of acute O(3) exposure. Moreover, elevated CO(2) did not ameliorate the adverse effects of acute O(3) dose on aspen and maple sprouts, in contrast to its ability to counteract the effects of long-term chronic exposure to lower O(3) levels.     

Multiple kinetic Langmuir modeling to predict the environmental behaviour of As(v) in soils

A soil with a relatively high Fe content (2.82% [w/w]) was loaded for up to one year with As(v) by equilibrating it with a solution containing 1000 mg l(-1) As(v) at a soil mass-to-solution ratio of 0.1 kg l(-1). The incorporation of As(v) into the soil and its distribution over the soil phases were monitored by sampling at strategic time intervals using an operationally defined five-step sequential extraction procedure (Wenzel et al., Anal. Chim. Acta, 2001, 436, 309) and subsequent As measurement. A multiple kinetic Langmuir model was developed to retrieve the dynamic parameters (adsorption and desorption rate constants, capacities and Langmuir equilibrium constants) for each of the soil phases by numerical fitting of the experimental adsorption data to the model. Under the equilibration conditions used the adsorption rate constants for all five operationally defined soil phases were very similar but the desorption rate constants decreased by a factor of ca. 150 from soil phase 1 (non-specifically sorbed As) to 5 (residual phases). This implies that As(v) incorporation "deeper" into the soil leads to stronger binding which is associated with the Langmuir equilibrium constants (adsorption rate constants/desorption rate constants). Equilibration of the soil with As(v) was complete in ca. 10 days with As(v) predominantly bound to soil phase 2 (specifically sorbed As) and soil phase 3 (amorphous and poorly crystalline hydrous oxides). X-Ray absorption spectroscopy techniques revealed that these binding characteristics may be related to adsorption of As(v) on Si- and/or Al-containing structures and natural hydrous iron oxide (HFO) surface sites, respectively. Since the model is independent of the initial As(v) concentration in the solution and the soil mass-to-solution ratio, the behaviour of the thus characterized soil-As(v) system can be predicted for a range of conditions. Simulations showed that in an accidental As(v) spill the soil studied would actively scavenge As(v) by instantaneous adsorption onto all soil phases followed by redistribution of As(v) from weaker binding sites to stronger ones over time.