Oxyanion flux characterization using passive flux meters: development and field testing of surfactant-modified granular activated carbon

We report here on the extension of Passive Flux Meter (PFM) applications for measuring fluxes of oxyanions in groundwater, and present results for laboratory and field studies. Granular activated carbon, with and without impregnated silver (GAC and SI-GAC, respectively), was modified with a cationic surfactant, hexadecyltrimethylammonium (HDTMA), to enhance the anion exchange capacity (AEC). Langmuir isotherm sorption maxima for oxyanions measured in batch experiments were in the following order: perchlorate>chromate>selenate, consistent with their selectivity. Linear sorption isotherms for several alcohols suggest that surfactant modification of GAC and SI-GAC reduced (approximately 30-45%) sorption of alcohols by GAC. Water and oxyanion fluxes (perchlorate and chromate) measured by deploying PFMs packed with surfactant-modified GAC (SM-GAC) or surfactant-modified, silver-impregnated GAC (SM-SI-GAC) in laboratory flow chambers were in close agreement with the imposed fluxes. The use of SM-SI-GAC as a PFM sorbent was evaluated at a field site with perchlorate contamination of a shallow unconfined aquifer. PFMs packed with SM-SI-GAC were deployed in three existing monitoring wells with a perchlorate concentration range of approximately 2.5 to 190 mg/L. PFM-measured, depth-averaged, groundwater fluxes ranged from 1.8 to 7.6 cm/day, while depth-averaged perchlorate fluxes varied from 0.22 to 1.7 g/m2/day. Groundwater and perchlorate flux distributions measured in two PFM deployments closely matched each other. Depth-averaged Darcy fluxes measured with PFMs were in line with an estimate from a borehole dilution test, but much smaller than those based on hydraulic conductivity and head gradients; this is likely due to flow divergence caused by well-screen clogging. Flux-averaged perchlorate concentrations measured with PFM deployments matched concentrations in groundwater samples taken from one well, but not in two other wells, pointing to the need for additional field testing. Use of the surfactant-modified GACs for measuring fluxes of other anions of environmental interest is discussed.     

Persistence and Dissipation Kinetics of Spiromesifen in Chili and Cotton

In a field study carried out at three different locations, the dissipation of spiromesifen on cotton and chili was studied and its DT₅₀, and DT₉₉ were estimated at each location. Spiromesifen was sprayed on chili at 96 and 192 g a.i. ha⁻¹ and cotton at 120 and 240 g a.i. ha⁻¹. Samples of chili fruits were drawn at 0, 1, 3, 5, 7, 10, 15, 21, 30 days after treatment and that of cotton seed and lint at first picking and harvest. Soil samples were drawn 30 days after treatment from 0 to 15 and 15 to 30 cm layer. Quantification of residues was done on GC–MS in Selected Ion Monitoring (SIM) mode in mass range 271–274 m/z. The LOQ of this method was found 0.033 μg g⁻¹, LOD being 0.01 μg g⁻¹. The DT₅₀ of spiromesifen when applied at recommended doses in chili fruits was found to be 2.18–2.40 days. Ninety-nine percent degradation was found to occur within 14.5–16.3 days after application. Residues of spiromesifen were not detected in cotton seed and lint samples at the first picking. In soil, no residues of spiromesifen were detectable 15 days after treatment.     

Bioavailable DDT residues in sediments: laboratory assessment of ageing effects using semi-permeable membrane devices

We describe the reduction in bioavailability of DDT in contaminated soil after it was incubated as sediment for 365 d. Bioavailability was assessed using semi-permeable membranes. Contaminated soils from three cattle dip sites, one spiked paired uncontaminated site, and one spiked OECD standard soil were studied. Sandy soil with residues of 1880 mg/kg summation operator DDT incurred since 1962, initially had 4.6% of summation operator DDT available, reducing to 0.6% following 365 d. Clay soil (1108 mg summation operator DDT/kg) had 4.1% initially available, reducing to 0.3% after 365 d. Freshly spiked soils had a greater amount of DDT initially available (10.9%), but this reduced to 1.5% by the end of the incubation. Of the DDT congeners, both o,p'-DDD and p,p'-DDD were most bioavailable in the soils, but also had the most significant decrease following incubation.     

A potential new commercial method for processing leather to reduce environmental impact

INTRODUCTION: Current leather processing method involves dehairing and fibre opening employing lime and sulphide, which results in higher negative impact on the environment due to its uncleanness. This method of dehairing and fibre-opening process accounts for nearly 70-80% biochemical oxygen demand and chemical oxygen demand (COD) in tannery wastewater and also the generation of H(2)S gas. MATERIALS AND METHODS: Hence, an attempt has been made to reduce the environmental impact of the leather processing through a biochemical approach, employing proteolytic enzyme and sodium metasilicate for performing the above process more cleanly. RESULTS AND DISCUSSION: The developed process exhibits significant reduction in environmental parametres such as COD and total solid loads by 55% and 25%, respectively. This method completely avoids the formation of lime sludge. CONCLUSION: The functional properties of the leathers are also on par with conventionally processed leathers. Further, the process seems to be commercially viable.     

Dynamic evaluation of a regional air quality model: Assessing the emissions-induced weekly ozone cycle

Air quality models are used to predict changes in pollutant concentrations resulting from envisioned emission control policies. Recognizing the need to assess the credibility of air quality models in a policy-relevant context, we perform a dynamic evaluation of the Community Multiscale Air Quality (CMAQ) modeling system for the “weekend ozone effect” to determine if observed changes in ozone due to weekday-to-weekend (WDWE) reductions in precursor emissions can be accurately simulated. The weekend ozone effect offers a unique opportunity for dynamic evaluation, as it is a widely documented phenomenon that has persisted since the 1970s. In many urban areas of the Unites States, higher ozone has been observed on weekends than weekdays, despite dramatically reduced emissions of ozone precursors (nitrogen oxides [NO_x] and volatile organic compounds [VOCs]) on weekends. More recent measurements, however, suggest shifts in the spatial extent or reductions in WDWE ozone differences. Using 18 years (1988–2005) of observed and modeled ozone and temperature data across the northeastern United States, we re-examine the long-term trends in the weekend effect and confounding factors that may be complicating the interpretation of this trend and explore whether CMAQ can replicate the temporal features of the observed weekend effect. The amplitudes of the weekly ozone cycle have decreased during the 18-year period in our study domain, but the year-to-year variability in weekend minus weekday (WEWD) ozone amplitudes is quite large. Inter-annual variability in meteorology appears to influence WEWD differences in ozone, as well as WEWD differences in VOC and NO_x emissions. Because of the large inter-annual variability, modeling strategies using a single episode lasting a few days or a few episodes in a given year may not capture the WEWD signal that exists over longer time periods. The CMAQ model showed skill in predicting the absolute values of ozone concentrations during the daytime. However, early morning NO_x concentrations were underestimated and ozone levels were overestimated. Also, the modeled response of ozone to WEWD differences in emissions was somewhat less than that observed. This study reveals that model performance may be improved by (1) properly estimating mobile source NO_x emissions and their temporal distributions, especially for diesel vehicles; (2) reducing the grid cell size in the lowest layer of CMAQ; and, (3) using time-dependent and more realistic boundary conditions for the CMAQ simulations.     

Dye house wastewater treatment through advanced oxidation process using Cu-exchanged Y zeolite: a heterogeneous catalytic approach

Catalytic wet hydrogen peroxide oxidation of an anionic dye has been explored in this study. Copper(II) complex of NN'-ethylene bis(salicylidene-aminato) (salenH2) has been encapsulated in super cages of zeolite-Y by flexible ligand method. The catalyst has been characterized by Fourier transforms infra red spectroscopy, X-ray powder diffractograms, Thermo-gravimetric and differential thermal analysis and nitrogen adsorption studies. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration on the oxidation of dye were studied. The results indicate that complete removal of color has been obtained after a period of less than 1h at 60 degrees C, 0.175M H2O2 and 0.3g l(-1) catalyst. More than 95% dye removal has been achieved using this catalyst for commercial effluent. These studies indicate that copper salen complex encapsulated in zeolite framework is a potential heterogeneous catalyst for removal of color from wastewaters.     

Distribution of pesticides, PAHs and heavy metals in prawn ponds near Kolleru lake wetland, India

This paper discussed the distribution of pesticides, polycyclic aromatic hydrocarbons (PAHs) and heavy metals in water, sediment and prawn from intensive prawn ponds (n=8) near the Kolleru lake wetland, India and assessed the quality of prawn for human consumption and also discussed the possible effects of these pollutants on pond environment and aquatic environment. The chemicals and other products used in prawn ponds near the Kolleru lake wetland were documented. The sediment, prawn and water samples were collected six times from selected prawn ponds during the production period of 3 months. Water samples were analyzed for selected physico-chemical parameters. The levels of pesticides, PAHs and heavy metals were found to decrease in the order sediment followed by prawn and water. The maximum concentrations of pesticides in sediment, prawn and water were alpha-BHC (174.2 microg g(-)(1)), gamma-BHC (234 microg g(-)(1)), malathion (256 microg g(-)(1)), chloripyrifos (198.5 microg g(-)(1)), endosulfan (238 microg g(-)(1)), dieldrin (19.6 microg g(-)(1)) and p,p'-DDT (128.6 microg g(-)(1)). Isodrin was found below detectable limit. The maximum concentrations of PAHs in sediment, prawn and water are anthracene (0.901 microg kg(-)(1)), fluranthene (0.601 microg kg(-)(1)), pyrene (0.786 microg kg(-)(1)), chrysene (0.192 microg kg(-)(1)), benzo(a)pyrene (0.181 microg kg(-)(1)) and benzo(ghi)perylene (227 microg kg(-)(1)). Benzo(e)pyrene, perylene, isomers of dibenzoanthracene and coronene were found below detectable limits. The maximum concentrations of heavy metals in sediment, prawn and water and also in prawn feed are Cu (791 microg g(-)(1)), Pb (270 microg g(-)(1)), Cd (1.07 microg g(-)(1)), Mn (4417 microg g(-)(1)), Ni (8.1 microg g(-)(1)), Co (5.8 microg g(-)(1)), Zn (1076 microg g(-)(1)), Cr (36.4 microg g(-)(1)), As (2.9 microg g(-)(1)), Se (6.3 microg g(-)(1)), Th (2.1 microg g(-)(1)) and Mo (0.762 microg g(-)(1)).     

岩溶流域土地利用变化对地下水水质的影响——以云南小江流域为例

利用1982、2003年土地利用现状图、地下水水质资料和监测数据,在GIS支持下,研究云南小江岩溶流域20年来的土地利用变化及其水文环境效应。结果表明:20年来,流域610.12km₂的土地利用面积发生变化;土地利用变化的主要过程是由未利用地向耕地和林地以及林地向耕地的转化;土地利用的空间格局发生很大变化,空间格局指数有不同程度的增加或减少;地下水水质的变化与土地利用变化表现出动态一致性,林地和未利用地转变为耕地后,地下水的总硬度、总碱度、pH值、SO42-、NO3-、Ca2+等离子值明显升高,并形成明显的高值区;1982年流域地下水以I、II、III级水质为主,而2003年流域却以IV、V级水质为主,地下水水质呈明显恶化趋势;流域地下水水质的变化与流域森林质量下降以及耕地扩张带来的化肥污染息息相关。     

Adsorption of anionic and nonionic surfactant mixtures from synthetic detergents on soils

Adsorption of anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) and nonionic surfactant (an alcohol ethoxylates with 12 carbons and 9 oxyethyl groups, A12E9) mixtures, widely used as the major constituents of synthetic detergents in China and become the most common pollutants in the environment, on soils was conducted to investigate the behavior of mixed surfactants in soils. The effects of addition order and mixing ratios of two surfactants, associated with pH and ion strength in solutions, on adsorptions were considered. The results show that saturated adsorption amount of SDBS and A12E9 on soils decreased respectively when A12E9 was added into soils firstly compared with that secondly, possibly resulting from the screening of A12E9 to part adsorption sites on soils and the hydrocarbon chain-chain interactions between SDBS and A12E9. The adsorption of SDBS and A12E9 on soils was enhanced each other at pre-plateau region of isotherms. At plateau region of isotherms, the adsorption of SDBS on soils decreased with the increase of molar fraction of A12E9 in mixed surfactant solutions, while that of A12E9 increased except the molar ratio of SDBS to A12E9 0.0:1.0. With the increase of pH in mixed surfactant solutions, adsorption amount of SDBS and A12E9 on soils decreased, respectively. The reduction of ion strength in soils resulted in the decrease of adsorption amount of SDBS and A12E9 on soils, respectively.