Non-linear regression model for spatial variation in precipitation chemistry for South India

Chemical composition of rainwater changes from sea to inland under the influence of several major factors – topographic location of area, its distance from sea, annual rainfall. A model is developed here to quantify the variation in precipitation chemistry under the influence of inland distance and rainfall amount. Various sites in India categorized as ‘urban’, ‘suburban’ and ‘rural’ have been considered for model development. pH, HCO₃, NO₃ and Mg do not change much from coast to inland while, SO₄ and Ca change is subjected to local emissions. Cl and Na originate solely from sea salinity and are the chemistry parameters in the model.Non-linear multiple regressions performed for the various categories revealed that both rainfall amount and precipitation chemistry obeyed a power law reduction with distance from sea. Cl and Na decrease rapidly for the first 100 km distance from sea, then decrease marginally for the next 100 km, and later stabilize. Regression parameters estimated for different cases were found to be consistent (R² ～ 0.8). Variation in one of the parameters accounted for urbanization. Model was validated using data points from the southern peninsular region of the country. Estimates are found to be within 99.9% confidence interval.Finally, this relationship between the three parameters – rainfall amount, coastline distance, and concentration (in terms of Cl and Na) was validated with experiments conducted in a small experimental watershed in the south-west India. Chemistry estimated using the model was in good correlation with observed values with a relative error of ～5%. Monthly variation in the chemistry is predicted from a downscaling model and then compared with the observed data. Hence, the model developed for rain chemistry is useful in estimating the concentrations at different spatio-temporal scales and is especially applicable for south-west region of India.     

Evaluation of vulnerability of Suillus variegatus and Suillus granulatus mushrooms to sequester mercury in fruiting bodies

This work determined the mercury (Hg) contents and bioconcentration potential of two Suillus mushrooms, and the probable dietary intake of this element from a mushroom meal. The determination of total Hg content of fungal and soil samples was performed using cold-vapour atomic absorption spectroscopy by a direct sample thermal decomposition coupled with gold wool trap of Hg and its further desorption and quantitative measurement at a wavelength of 253.7 nm. The median values of Hg contents (mg kg^?1 dry biomass) in 213 specimens of S. variegatus from 12 background areas varied widely from 0.087 to 0.51 for caps and from 0.041 to 0.24 for stipes. In 52 specimens of S. granulatus, the Hg contents ranged from 0.30 to 0.41 for caps and from 0.058 to 0.14 for stipes. Both species could be classified as moderate accumulators of Hg and the median bioconcentration factor values ranged from 7.0 to 14 (caps) and 2.1 to 13 (stipes) for S. variegatus and 9.5 (caps) and 1.3 (stipes) for S. granulatus. The estimated intake rates of Hg with the consumption of 300-g caps were from 0.0026 to 0.015 per capita or from 0.000037 to 0.00022 mg kg^?1 body mass and this do not indicate any cause for concern associated with eating a meal once or more in a week during the mushrooming season.     

Historic emissions of fluorotrichloromethane (CFC-11) based on a market survey

Releases of CFCs occur promptly from applications such as aerosol sprays, or over a period of several years from refrigeration and air conditioning or more slowly still from use as blowing agents for closed cell plastic foams. As a consequence of the Montreal Protocol, the emissions have fallen and their pattern is continuing to change. To help quantify these changes the emissions from closed cell foam blowing have been re-examined in a comprehensive market survey, developing a lifecycle assessment for each foam type, production method and foaming agent.The original model for the time series of emissions from foam applications was shown to remain a robust representation in general terms. There is an “immediate” loss when the foam is manufactured, a slow emission from the foam itself during use and a loss on disposal of the artefact made with the foam. The original model used an initial loss rate of 10% and a subsequent loss of 4.5% yr⁻¹ over 20 yr.The new survey showed a wide range of initial and service loss rates. Immediate release ranges from 95% down to 4%; similarly, the rate of loss during service varies from 0.5% to 5% yr⁻¹ and the service lifetimes of the artefacts made with the foams varies from 12 to 50 yr. The apparent emission function, in terms of the mean value of the annual fractional release from the bank of CFC-11 residing in foams, was calculated from the survey to be 0.043±0.008 over 28 yr. There is a small and non-significant fall in this function with time; so that over the last ten years of the data record the more appropriate value is 0.0366±0.0008. However, up to the early 1990s, it is the original emission function that is consistent with the observed atmospheric concentrations. Thenceforth this function seriously overpredicts the concentrations but, if the new emissions function for foams is used from 1993 onwards in conjunction with the original emission functions for all other uses, the fit becomes better. This suggests that the emission functions for prompt and short term releases remain valid and should be coupled with the new function to calculate emissions of CFC-11 or other fluorocarbon foam blowing agents from the early 1990s onwards.     

Concentration and fate of persistent organochlorine pesticides in estuarine sediments using headspace solid-phase microextraction

The concentration and fate of persistent organochlorine pesticides (OCPs) in estuarine surface sediments in Erh-jen and Lan-yang rivers, Taiwan were investigated using headspace solid-phase microextraction (HSSPME) method to evaluate the possible pollution potential and guideline for OCP concentrations in Taiwan. The HSSPME method exhibits a good analytical performance with low detection limits for OCP determination in sediment. In addition, results obtained using the developed HSSPME method were in good agreement with those obtained using Soxhlet extraction in a certified sample. The developed analytical method was further applied to the determination of concentrations of OCP residues in surface sediments from the estuaries of the selected rivers in Taiwan. A total of 20 surface sediments from each river was collected from 10 sampling stations. The total OCP concentrations in sediments from Erh-jen River ranged from 0.17 to 5.04 ng/g-dw with the mean values of 0.25–1.24 ng/g-dw for HCHs, 0.10–0.89 ng/g-dw for cyclodienes and 0.16–0.64 ng/g-dw for DDTs. The concentrations of OCPs in sediments from Lan-yang River were in the range 0.37–0.9 ng/g-dw with an average of lower than 0.5 ng/g-dw. HCHs and DDTs were abundant in the estuarine sediments from the selected rivers. Results obtained in this study show that the origin of OCPs in the surface sediments from Erh-jen River is a combination of erosion of the weathered soils and long-range atmospheric transport, while the OCP concentrations found in Lan-yang River could be regarded as the background levels of OCPs in Taiwan.     

Early atmospheric detection of carbon dioxide from carbon capture and storage sites

The early atmospheric detection of carbon dioxide (CO₂) leaks from carbon capture and storage (CCS) sites is important both to inform remediation efforts and to build and maintain public support for CCS in mitigating greenhouse gas emissions. A gas analysis system was developed to assess the origin of plumes of air enriched in CO₂, as to whether CO₂ is from a CCS site or from the oxidation of carbon compounds. The system measured CO₂ and O₂ concentrations for different plume samples relative to background air and calculated the gas differential concentration ratio (GDCR = ?ΔO₂/ΔCO₂). The experimental results were in good agreement with theoretical calculations that placed GDCR values for a CO₂ leak at 0.21, compared with GDCR values of 1–1.8 for the combustion of carbon compounds. Although some combustion plume samples deviated in GDCR from theoretical, the very low GDCR values associated with plumes from CO₂ leaks provided confidence that this technology holds promise in providing a tool for the early detection of CO₂ leaks from CCS sites. Implications: This work contributes to the development of a cost-effective technology for the early detection of leaks from sites where CO₂ has been injected into the subsurface to enhance oil recovery or to permanently store the gas as a strategy for mitigating climate change. Such technology will be important in building public confidence regarding the safety and security of carbon capture and storage sites.     

Polycyclic aromatic hydrocarbon emission from straw burning and the influence of combustion parameters

A simulated burning experiment was conducted in a tubular furnace system to examine the emission of polycyclic aromatic hydrocarbons (PAHs) from the burning of rice and bean straw, and the influence of combustion parameters was investigated. Total emission amounts of 16 PAHs (∑PAHs) from the burning of rice and bean straw ranged from 9.29 to 23.6 μg g^?1 and from 3.13 to 49.9 μg g^?1, respectively, which increased with the increase of temperatures from 200 to 700 °C. The contribution of combustion to individual PAH yields was about 80.6–100%, which was generally increased with the increase of burning temperature. Moisture content in straw had a negative effect on PAH formation, especially on PAHs with low molecular weight. ∑PAHs emission amounts decreased by 78.2% for bean straw with a moisture content of 30% in comparison with that for dried straw. In addition, PAH emission amounts increased with the increase of O₂ content in supplied air and then decreased, which showed a maximum emission at O₂ content of 40%. The source fingerprint of PAHs in emission from straw burning was established, which showed that naphthalene accounted for 35.0 ± 7.4% of ∑PAHs. Based on the experimental data, emission amounts of ∑PAHs from the burning of rice and bean straw were estimated to be 320–357 and 32.5–76.0 tons to ambient air per year in China, respectively.     

Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.     

A sensitive diffusion sampler for the determination of volatile organic compounds in ambient air

We developed a diffusive sampling device (DSD-voc) for volatile organic compounds (VOCs) which is suitable for collection of low level VOCs and analysis with thermal desorption. This sampling device is composed of two parts, an exposure part made of a porous polytetrafluoroethylene (PTFE) filter, and an analysis part made of stainless-steel tubing. The DSD-voc collects VOCs through the mechanism of molecular diffusion. Collection is controlled by moving the adsorbent from the exposure part to the analysis part by changing the posture of the DSD-voc. Adsorbates in the DSD-voc were analyzed by GC/MS with a thermal desorption cold trap injector (TCT). The TCT has the advantage of being able to accept the entire quantity of VOCs. We connected a condenser between the DSD-voc and the trap tube to prevent moisture from freezing in the trap tube when the sampler was packed with strong adsorbent. We also examined the desorption efficiency for VOCs from several types of adsorbents (Carboxen^TM 1000, Carbosieve^TM G, Carbosieve S III, Carbotrap^TM B, and activated carbon) over a wide range of temperatures. Carboxen 1000 was suitable for the determination of VOCs with a low boiling point range, from CFC12 to hexane, while Carbotrap B was suitable for VOCs from hexane to 1,4-dichlorobenzene. The limits of detection with Carboxen 1000 and Carbotrap B were 0.036–0.046 and 0.0035–0.014 ppb, respectively, for a sampling duration of 24 h. Coefficients of variation for concentrations of major VOCs ranged from 3.8 to 14%. It is possible to estimate atmospheric VOCs at sub-parts per billion (sub-ppb), with high sensitivity, by using both adsorbents in combination.     

Anthropogenic sulphate aerosol from India: estimates of burden and direct radiative forcing

A one-box chemical-meteorological model had been formulated to make preliminary estimates of sulphate aerosol formation and direct radiative forcing over India. Anthropogenic SO₂ emissions from India, from industrial fuel use and biomass burning, were estimated at 2.0 Tg S yr^-1 for 1990 in the range of previous estimates of 1.54 and 2.55 Tg S yr ^-1 for 1987. Meteorological parameters for 1990 from 18 Indian Meteorological Department stations were used to estimate spatial average sulphate burdens through formation from SO₂ reactions in gas and aqueous phase and removal by dry and wet deposition. The hydrogen peroxide reaction was found dominating for undepleted oxidant-rich conditions. Monthly mean sulphate burdens ranged from 2–10 mg m^-2 with a seasonal variation of winter–spring highs and summer lows in agreement with previous GCM studies. The sulphate burdens are dominated by sulphate removal rates by wet deposition, which are high in the monsoon period from June–November. Monthly mean direct radiative forcing from sulphate aerosols is high (−3.5 and −2.3 W m^-2) in December and January, is moderate (−1.3 to −1.5 W m^-2) during February to April and November and low (−0.4 to −0.6 W m^-2) during May to October also in general agreement with previous GCM estimates. This model, in reasonable agreement with detailed GCM results, gives us a simple tool to make preliminary estimates of sulphate burdens and direct radiative forcing.     

Hg Vapor Emission from Broken Compact Fluorescent Lamps (CFLs) in an Acrylic Chamber

The United States Environmental Protection Agency/Environmental Response Team (US EPA/ERT), in collaboration with St. John's College, Dr. B. R. Ambedkar University, Agra, India, is conducting a study to determine Hg vapor emission rates resulting from broken compact fluorescent lamps (CFLs) in a residential setting. The overall objectives of the study are to determine Hg vapor emission data and provide homeowners with cleanup procedures and disposal options for broken CFLs. Most of the currently available CFLs in the US market are manufactured in China for US companies. Several different types of CFLs were purchased from local stores and their Hg content was determined. Based on previous studies, such as the 2011 study by Singhvi and colleagues, five popular spiral CFLs were selected for emission studies in an acrylic chamber. This study found that Hg vapor emissions from CFLs may be significantly greater than those from beads of liquid Hg with weights comparable to the Hg content of the CFLs. The average 24-hour Hg loss into the atmosphere from CFLs broken on a plastic surface ranged from 0.6% to 22% of the bulb content, while that for CFLs broken on carpet ranged from 2.6% to 28%. Projections for a 12 foot × 9.33 foot × 8 foot (25.4 m³) room based on the chamber measurements in this study indicate that CFL breakage in some household settings may produce 24-hour Hg concentrations above the 2000 Agency for Toxic Substances and Disease Registry (ATSDR) minimum risk level (MRL) of 0.2 μg/m³, for typical air exchange rates. This study also indicates that Hg emission may not be proportional to exposed surface area based on experiments using liquid Hg with different surface areas.     

Chemical characteristics of long-range transport aerosol at background sites in Korea

In this study, background concentration sites of Deokjeok and Gosan, which were deemed suitable for monitoring the impact of long-range transported air pollutants, were selected. An investigation of the source types of pollutants, their locations, and relative quantitative contributions to the particulate concentrations at both sites using appropriate methodologies to make initial estimations was conducted. Episodic measurements of PM_2.5, PM₁₀, and size distribution, along with its ion and carbon components were performed from 2005 to 2007, and a comprehensive analysis of the results was conducted utilizing back trajectory analysis. As for frequency of wind direction, it was quite apparent that the two sites are heavily influenced by air masses originating from the eastern and northern regions of China. For PM_2.5 and PM₁₀, the mass concentrations from north and east China were higher than other cases, originating from the ocean. In the northerly-wind case, meteorological properties for Deokjeok and Gosan and the influence of carbon emissions from northwest Korea resulted in a changing of air mass properties during transport. As was the case with mass concentration, the highest contribution for ionic and carbon components of PM_2.5 and PM₁₀ for both sites appeared for the westerly wind case. A specially high relative contribution, greater than 1.4 times, was apparent in the secondary aerosol case because of a large influence of long-range transported pollutants from east China. Carbon components exhibited different behaviors for the northerly and westerly wind cases compared with secondary aerosol. The major reason for this discrepancy appears to be the carbon emissions from northwest Korea.     

Trends and sources of particulate matter in the Superstition Wilderness using air trajectory and aerosol cluster analysis

Ambient aerosols adversely affect human health and visibility and impact climate. Identification of sources of particulate matter and its precursors is necessary for developing control strategies. The goal of this research is to utilize long-term speciated particulate matter data and back-trajectory cluster analyses to determine trends and sources of particulate matter in the Superstition Wilderness, a rural area east of Phoenix, Arizona. Twenty-four hour back-trajectories were calculated for every hour of every 24-h particulate matter sample obtained by IMPROVE from 1991 to 2004. Days that included back-trajectories with considerable spatial variance were excluded from further analyses. To minimize uncertainties inherent in single trajectories, all calculated trajectories for each sampling day were averaged to represent the air mass sampled during that day. Cluster analysis of trajectories identified four unique regions, including a region with Phoenix, a region with copper smelters, and one with coal-fired power plants. Yearly averages of sulfate, nitrate, soil, and carbon concentrations were calculated for each region. Statistically significant trends in species concentrations by region and independent of region and differences in concentrations between regions were examined.Sulfate concentrations from the region with smelters were higher than other regions but decreased during the study period. Emissions data from the smelters indicate that much of the sulfate from the region was due to the smelters. The overall 2.2% year⁻¹ decrease in sulfate concentrations at TNM is likely due to decreased emissions from the copper smelters. A 3.6% year⁻¹ increase in nitrate concentrations was driven largely by increasing NO_x concentrations from Phoenix and to a lesser extent the region southwest of the site which includes Tucson and suburban/urban areas between Phoenix and Tucson. Soil concentrations were higher from regions with deserts than the region without desert. This method could not identify trends or source regions of carbonaceous aerosols at this site.     

Pesticide residues in Indian raw honeys,an indicator of environmental pollution

Honey has multifaceted beneficial properties, but polluted environment and unapproved apicultural practices have led to its contamination. In this study, QuEChERS method followed by chromatographic analysis by GC-μECD/FTD and GC-MS was validated and used for determination of 24 pesticides in 100 raw honey samples from various floral origins of Northern India. Matrix-matched calibrations showed that the method was selective and linear (r²?>?0.99) with detection limit <?9.1 ng g^?1 for all the studied pesticides except for monocrotophos (21.3 ng g^?1). The average recoveries at different fortification levels ranged from 86.0 to 107.7% with relative standard deviation <?20%. Pesticide residues were detected in 19.0% samples, and most prevalent compounds detected were dichlorvos in 6.0% samples followed by monocrotophos (5.0%), profenofos (5.0%), permethrin (4.0%), ethion (3.0%), and lindane (3.0%) with concentrations ranging from 58.8 to 225.5, from 96.0 to 430.1, from 14.6 to 43.2, from 27.8 to 39.6, from 25.6 to 28.0, and from 19.6 to 99.2 ng g^?1, respectively. Honey samples originating from cotton, sunflower, and mustard crops (33.3%) that tested positive for pesticide residues were found to be significantly higher (p?<?0.05) than the honey originating from natural and fruity vegetation (13.5%). Therefore, considering the contamination of environmental compartments due to extensive application of pesticides in the study area and their potential for subsequent transfer to honey by the expeditious bees, the results of present study proclaim that honey may be used as an indicator of environmental pollution. Further, estimated daily intakes of all contaminants were found to be at levels well below their acceptable daily intakes suggesting that consumption of honeys at current levels does not pose deleterious effects on human health. However, precautionary measures should always be taken considering the customary honey feeding in infants and cumulative effect of these chemicals in the foreseeable future.     

Ozone Measurements in South Carolina Using Passive Samplers

Abstract

Passive samplers with two different collection substrates were used to obtain an average ozone concentration for 1 month during the summer of 2002 for each South Carolina county. One sampler contained a filter coated with indigo carmine, whose color fades when exposed to ozone. The fading was measured by reflectance spectroscopy. The other sampler contained filters that were coated with nitrite, which is oxidized to nitrate when exposed to ozone. The nitrate was measured by ion chromatography.

Calibration curves were developed for the two methods by comparing color fading from indigo carmine and nitrate ion concentration from the nitrite filter with ambient ozone concentration measured by a co-located reference continuous UV ozone analyzer. These curves were used to calculate integrated ozone concentrations for samplers distributed across South Carolina.

Using the indigo carmine method, the average ozone concentrations ranged from 21 to 64 ppb (average = 46 ± 7.9 ppb, n = 58) across the 46 counties in the state during one summer month of 2002. Concentrations for the same time period from the nitrite-coated filters ranged from 23 to 62 ppb (average = 41 ± 8.1 ppb, n = 58). Also for the same time period, the 23 continuous UV photometric ozone monitors operated by the South Carolina Department of Health and Environmental Control at sites within 10 miles of some of the passive monitors showed ozone concentrations ranging from 28 to 50 ppb (average = 39 ± 6.3 ppb, n = 22).     

Optimization of analytical methods to improve detection of erythromycin from water and sediment

Analytical methods to improve the detection of erythromycin in water and sediment were developed to optimize for erythromycin's recovery of extractable and bound residues from the aquatic environment. The objective of this study was to determine optimal recovery of erythromycin from water and sediment to improve its detection in environmental samples through solid-phase extraction (SPE) and sediment-extraction methods. SPE methods examined included previously reported methods for macrolide and sulfonamide antibiotics with erythromycin recoveries ranging from 75.5 % to 94.7 %. Extraction of erythromycin was performed from sand employing various solvents and buffers to determine the best method for extraction from two sandy loam pond sediments. Various extraction times were also examined, and all extraction procedures were performed in duplicate. The greatest recovery of ¹⁴C-erythromycin in the Iowa sediment was 84 % using 0.3 M ammonium acetate at pH 4.2: acetonitrile (15:85, v/v) solution. The Oklahoma sediment yielded the greatest recovery of ¹⁴C-erythromycin at 86.7 % with 0.3 M ammonium acetate at pH 7: acetonitrile (30:70, v/v) with a 60-minute shake time. The present results demonstrate improved extraction methods for enhancing the accuracy of erythromycin detection from environmental samples.     

Chemical composition of fine particles from incense burning in a large environmental chamber

 This study is aimed to characterize the major chemical compositions of PM_2.5 from incense burning in a large environmental chamber. Chemical analyses, including X-ray fluorescence for elemental species, ion chromatography for water soluble inorganic species (chloride, nitrate, sulfate, sodium, potassium, ammonium) and thermal/optical reflectance analysis for carbon species were carried out for combustion of three incense categories (traditional, aromatic and church incense). The average concentrations from incense burning ranged from 139.8 to 4414.7 μg m⁻³ for organic carbon (OC), and from 22.8 to 74.0 μg m⁻³ for elemental carbon (EC), respectively. The average OC and EC concentrations in PM_2.5 of three incense categories were in the order of church incense>traditional incense>aromatic incense. OC/EC ratios ranged from 7.0 to 39.1 for the traditional incense, with an average of 21.7; from 3.2 to 11.9 for the aromatic incense, with an average of 7.7. The concentrations of Cl⁻, SO₄²⁻, Na⁺ and K⁺ were highly variable. On average, the inorganic ion concentration sequence was traditional incense>church incense>aromatic incense. The profiles for elements were dominated by Na, Cl and K. In general, the major components in PM_2.5 fraction from incense burning are OC (especially OC2, OC3 and OC4), EC and K.     

连续流反应器污水硝化过程中的N2O释放

污水生物脱氮硝化阶段是温室气体一氧化二氮(N2O)的重要释放源。采用连续流反应器在2种进水氨氮(NH4-N,低氮反应器60 mg/L和高氮反应器180 mg/L)浓度条件下驯化硝化菌,并研究了不同初始NH4-N浓度和不同初始亚硝酸盐(NO2-N)浓度条件下所驯化硝化菌释放N2O的特征。结果表明在反应器运行过程中2个反应器释放N2O较少,均小于去除NH4-N浓度的0.01%;N2O的释放均随着初始NH4-N浓度或初始NO2-N浓度的升高而增加;不同初始NH4-N浓度条件下,低氮反应器驯化硝化菌的N2O释放率在0.51%~1.40%之间,高氮反应器驯化硝化菌在0.29%~1.27%之间;不同初始NO2-N浓度条件下,低氮反应器驯化硝化菌的N2O释放率在1.38%~3.78%之间,高氮反应器驯化硝化菌在1.16-5.81%之间。     

Performances of mesophilic anaerobic digestion systems treating poultry mortalities

Abstract

A closed‐loop anaerobic digestion system consisting of a leachbed (LB) and an upflow anaerobic sludge blanket (UASB) was tested as an alternative for the disposal of poultry mortalities. This paper compares the performances of three LB‐UASB treatment systems with different initial moisture contents in the LBs. Each LB was loaded with one chicken and 5, 10 or 18 liters of water. The LBs initially carried out the hydrolysis/acidification phase while the UASBs the methanogenesis phase. Due to repeated inoculation by the UASBs, the LBs with 10 and 18 liters of water started producing methane on day 5, while the one with 5 liters of water on day 19. However, methane production rates were low before day 40 for the LB with 10 liters of water and day 60 for the other LBs. Methane production gradually improved as the LBs continued to receive ungranulated sludge from the UASBs. The LBs eventually became balanced methane reactors. Continued balanced fermentation in the LBs resulted in leachates with very low substrate concentrations that could no longer support high‐rate methanogenesis in the UASBs. Consequently, methane production rates from the UASBs decreased quickly while that from the LBs reached peak levels. Cumulative methane production from each LB eventually exceeded that from its connecting UASB. After 118 days of digestion, 414, 437 and 470 liters of methane were produced from the three systems, respectively. Cumulative methane production from the LBs with 5 and 18 liters of water accounted for 63% of the total methane produced from their respective systems. The LB with 10 liters of water produced 75% of the total methane from that system. Methane yields ranged from 0.485 to 0.554 m³ (Kg TS) ¹. About 86% of the initial dry weight was biodegraded. All three systems performed very well with little operational problems. Overall, the system that started with 10 liters of water in the LB performed the best. Strategy for enhancing system performances and implementing farm applications are discussed.     

Hydroxyl (OH) radical production rates in snowpacks from photolysis of hydrogen peroxide (H2O2) and nitrate (NO3−)

Atmospheric chemistry directly above snowpacks is strongly influenced by ultraviolet (UV) radiation initiated emissions of chemicals from the snowpack. The emission of gases from the snowpack to the atmosphere is in part due to chemical reactions between hydroxyl radical, OH (produced from photolysis of hydrogen peroxide (H₂O₂) or nitrate (NO₃⁻)) and impurities in the snowpack. The work presented here is a radiative-transfer modelling study to calculate the depth-integrated production rates of hydroxyl radical from the photolysis of hydrogen peroxide and nitrate anion in snow for four different snowpacks and for solar zenith angles 30°–90°. This work also demonstrates the importance of hydrogen peroxide photolysis to produce hydroxyl radical relative to nitrate photolysis with (a) different snowpacks, (b) different ozone column depths, and (c) snowpack depths. The importance of hydrogen peroxide photolysis over nitrate photolysis for hydroxyl radical production increases with increasing depth in snowpack, column ozone depth, and solar zenith angle. With a solar zenith angle of 60° the production of hydroxyl radical from hydrogen peroxide photolysis accounts for 91–99% of all hydroxyl radical production from hydrogen peroxide and nitrate photolysis.     

Water pressure head and temperature impact on isoxaflutole degradation in crop residues and loamy surface soil under conventional and conservation tillage management

Laboratory incubations were performed in order to evaluate the dissipation of the proherbicide isoxaflutole in seedbed layer soil samples from conventional and conservation tillage systems and in maize and oat residues left at the soil surface under conservation tillage. The effects of temperature and water pressure head on radiolabelled isoxaflutole degradation were studied for each sample for 21 d. Mineralisation of isoxaflutole was low for all samples and ranged from 0.0% to 0.9% of applied ¹⁴C in soil samples and from 0.0% to 2.4% of applied ¹⁴C in residue samples. In soil samples, degradation half-life of isoxaflutole ranged from 9 to 26 h, with significantly higher values under conservation tillage. In residue samples, degradation half-life ranged from 3 to 31 h, with significantly higher values in maize residues, despite a higher mineralisation and bound residue formation than in oat residues. Whatever the sample, most of the applied ¹⁴C remained extractable during the experiment and, after 21 d, less than 15% of applied ¹⁴C were unextractable. This extractable fraction was composed of diketonitrile, benzoic acid derivative and several unidentified metabolites, with one of them accounting for more than 17% of applied ¹⁴C. This study showed that tillage system design, including crop residues management, could help reducing the environmental impacts of isoxaflutole.