Assessment of boscalid and pyraclostrobin disappearance and behavior following application of effective microorganisms on apples

ABSTRACT

The aim of this study is to assess the disappearance of boscalid (IUPAC name: 2-chloro-N-[2-(4-chlorophenyl)phenyl]pyridine-3-carboxamide) and pyraclostrobin (IUPAC name: methyl N-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-N-methoxycarbamate) residues in apple fruit, and to verify whether an organic fertilizer enriched with strains of antagonistic microorganisms can reduce pesticide residue levels. Field trials were conducted in a commercial orchard on apples of the Gloster variety, during 21 days after the treatment with Bellis 38 WG and the subsequent application of Zumba Plant formulation containing Bacillus spp., Trichoderma spp. and Glomus spp. In control samples, the decrease rate of boscalid and pyraclostrobin residue levels followed an exponential function, described by formulae R_t = 0.2824e^?0.071t and R_t = 0.1176e^?0.060t, with the coefficient of determination of r² = 0.8692 and r² = 0.9268, respectively. These levels dropped to half (t_1/2) of their initial values after 9.8 and 11.5 days, respectively. The treatment with Zumba Plant resulted in a reduction in boscalid and pyraclostrobin residue levels by 52% and 41%, respectively. The results of this study are of importance for horticulture sciences and for producers of apples using plant protection products (PPPs).     

An hourly PM10 diagnosis model for the Bilbao metropolitan area using a linear regression methodology

There is extensive evidence of the negative impacts on health linked to the rise of the regional background of particulate matter (PM) 10 levels. These levels are often increased over urban areas becoming one of the main air pollution concerns. This is the case on the Bilbao metropolitan area, Spain. This study describes a data-driven model to diagnose PM10 levels in Bilbao at hourly intervals. The model is built with a training period of 7-year historical data covering different urban environments (inland, city centre and coastal sites). The explanatory variables are quantitative—log [NO₂], temperature, short-wave incoming radiation, wind speed and direction, specific humidity, hour and vehicle intensity—and qualitative—working days/weekends, season (winter/summer), the hour (from 00 to 23 UTC) and precipitation/no precipitation. Three different linear regression models are compared: simple linear regression; linear regression with interaction terms (INT); and linear regression with interaction terms following the Sawa’s Bayesian Information Criteria (INT-BIC). Each type of model is calculated selecting two different periods: the training (it consists of 6 years) and the testing dataset (it consists of 1 year). The results of each type of model show that the INT-BIC-based model (R ²?=?0.42) is the best. Results were R of 0.65, 0.63 and 0.60 for the city centre, inland and coastal sites, respectively, a level of confidence similar to the state-of-the art methodology. The related error calculated for longer time intervals (monthly or seasonal means) diminished significantly (R of 0.75–0.80 for monthly means and R of 0.80 to 0.98 at seasonally means) with respect to shorter periods.     

Simultaneous removal of PCDD/Fs and mercury by activated carbon from a full-scale MSW incinerator in southeast China

This study emphasized on the removal performance of polychlorinated-ρ-dibenzodioxins and dibenzofurans (PCDD/Fs) and mercury by different activated carbon injection (ACI) rates from a full-scale (700 t/d) MSW incinerator. The result exhibited that the emission standard of PCDD/Fs and mercury could be met when the ACI rate reached 50 mg/Nm³ and 30 mg/Nm³, respectively. Lower chlorinated PCDD/Fs and PCDFs showed higher removal efficiencies compared with highly chlorinated PCDD/Fs and PCDDs, which could be attributed to the larger competitiveness of highly volatile congeners in AC adsorption than the lower volatile ones. AC turned out to have different adsorption selectivity for CP-routes PCDD/Fs congeners, among which 1379-TCDD was preferred to be absorbed while others exhibited little or poor selectivity for AC adsorption. The removal efficiency of PCDD/Fs was positively correlated with ACI rate at 99% confidence interval with a linear relationship (R²?=?0.98). Also, the outlet concentration of mercury decreased with the increase of ACI rate in a nearly linear function (R²?=?0.96). These results will be meaningful for the rational use of AC for pollutants control.

     

Dissolution behavior of representative elements from red mud (RM) by leaching with titanium white waste acid (TWWA)

Titanium white waste acid (TWWA) was used to dissolve the representative elements from red mud (RM) to achieve the goal of “treating waste with waste.” The leaching parameters on the leaching efficiency of Na, Sc, and Al were investigated, in which the analysis of XRD and SEM–EDS on RM and leaching residue was performed. The leaching kinetics of Na, Sc, and Al was studied with unreacted shrinking core model (USCM). The results show that the dealkalization efficiency was close to 100%, and the leaching efficiency of Sc and Al was 82% and 75%, respectively. Cancrinite was dissolved from RM, and then the elements such as Na, Al, and Ca reacted with H₂SO₄ of TWWA. Na existed in the leaching liquor in the form of ions. Ca reacted with sulfuric acid to form anhydrite, which existed in the leaching residue. The particles of RM became smaller and dispersed with each other by acid leaching. The leaching apparent activation energy of Na, Sc, and Al was 4.947 kJ/mol, 6.361 kJ/mol, and 31.666 kJ/mol, respectively. The leaching kinetic equation of Na, Sc, and Al was 1???(1???a)^2/3?=?0.084·exp[??595.05/T]·t by external diffusion, 1???2a/3???(1???a)^2/3?=?0.021·exp[??765.16/T]·t by internal diffusion, and ln(1???a)/3?+?(1???a)^?2/3 – 1?=?67.12·exp[??3808.8/T]·t by joint action, respectively.

     

Coupling of titania with multiwall carbon nanotubes for decomposition of gas-phase pollutants under simulated indoor conditions

This study synthesized multiwall carbon nanotube (MWNT)–titania (TiO₂) composites and examined their characteristics and photocatalytic performance for the cleaning of gas-phase benzene, toluene, ethyl benzene, and o-xylene (BTEX) under simulated indoor conditions. Optical and spectral surveys of the as-synthesized composite confirmed that the TiO₂ nanoparticles were bound intimately to the MWNT networks. The photocatalytic performance was evaluated using an annular-type reactor inner-coated with MWNT–TiO₂ or Degussa P25 TiO₂. The composite revealed gas removal ability superior to that of stand-alone TiO₂. This composite was also less affected by humidity during toluene decomposition compared to the previous result obtained from a stand-alone TiO₂. Unlike another previous result obtained from the TiO₂, the performance of the composite was not affected by changes in input concentration (IC) within a simulated indoor air quality range (0.1–1.0 ppm) but it decreased significantly when the IC was increased to 5 and 10 ppm. As the flow rate was decreased from 4.0 to 1.0 L min^?1, the average efficiency for the target compounds increased to 95% or ～100%. The MWNT–TiO₂ composite could be applied effectively to the decomposition for BTEX under certain simulated indoor conditions.

Implications: Unlike water applications, there are few reports of gas-phase applications of multiwall carbon nanotubes (MWCNT)–TiO₂ composites. This study found that MWCNT–TiO₂ composites showed performance in the removal of toxic gaseous aromatic superior to that of stand-alone TiO₂. In addition, the pollutant degradation efficiency of the composite was less affected by humidity than for a stand-alone TiO₂ unit within a simulated indoor relative humidity range. Moreover, unlike the TiO₂ unit, the composite's performance was not affected by variations in the input concentrations within the simulated indoor air quality (IAQ) range. In addition, the decomposition efficiencies increased to 100% with decreasing flow rate.     

Remote estimation of phycocyanin (PC) for inland waters coupled with YSI PC fluorescence probe

Nuisance cyanobacterial blooms degrade water resources through accelerated eutrophication, odor generation, and production of toxins that cause adverse effects on human health. Quick and effective methods for detecting cyanobacterial abundance in drinking water supplies are urgently needed to compliment conventional laboratory methods, which are costly and time consuming. Hyperspectral remote sensing can be an effective approach for rapid assessment of cyanobacterial blooms. Samples (n?=?250) were collected from five drinking water sources in central Indiana (CIN), USA, and South Australia (SA), which experience nuisance cyanobacterial blooms. In situ hyperspectral data were used to develop models by relating spectral signal with handheld fluorescence probe (YSI 6600 XLM-SV) measured phycocyanin (PC in cell/ml), a proxy pigment unique for indicating the presence of cyanobacteria. Three-band model (TBM), which is effective for chlorophyll-a estimates, was tuned to quantify cyanobacteria coupled with the PC probe measured cyanobacteria. As a comparison, two band model proposed by Simis et al. (Limnol Oceanogr, 50(11): 237–245, 2005; denoted as SM05) was paralleled to evaluate TBM model performance. Our observation revealed a high correlation between measured and estimated PC for SA dataset (R ²?=?0.96; range: 534–20,200 cell/ml) and CIN dataset (R ²?=?0.88; range: 1,300–44,500 cell/ml). The potential of this modeling approach for imagery data were assessed by simulated ESA/Centinel3/OLCI spectra, which also resulted in satisfactory performance with the TBM for both SA dataset (RMSE %?=?26.12) and CIN dataset (RMSE %?=?34.49). Close relationship between probe-measured PC and laboratory measured cyanobacteria biovolume was observed (R ²?=?0.93, p?<?0.0001) for the CIN dataset, indicating a stable performance for PC probe. Based on our observation, field spectroscopic measurement coupled with PC probe measurements can provide quantitative cyanobacterial bloom information from both relatively static and flowing inland waters. Hence, it has promising implications for water resource managers to obtain information for early warning detection of cyanobacterial blooms through the close association between probe measured PC values and cyanobacterial biovolume via remote sensing modeling.     

Forecasting hourly PM<Subscript>10</Subscript> concentration in Cyprus through artificial neural networks and multiple regression models: implications to local environmental management

In the present work, two types of artificial neural network (NN) models using the multilayer perceptron (MLP) and the radial basis function (RBF) techniques, as well as a model based on principal component regression analysis (PCRA), are employed to forecast hourly PM₁₀ concentrations in four urban areas (Larnaca, Limassol, Nicosia and Paphos) in Cyprus. The model development is based on a variety of meteorological and pollutant parameters corresponding to the 2-year period between July 2006 and June 2008, and the model evaluation is achieved through the use of a series of well-established evaluation instruments and methodologies. The evaluation reveals that the MLP NN models display the best forecasting performance with R ² values ranging between 0.65 and 0.76, whereas the RBF NNs and the PCRA models reveal a rather weak performance with R ² values between 0.37-0.43 and 0.33-0.38, respectively. The derived MLP models are also used to forecast Saharan dust episodes with remarkable success (probability of detection ranging between 0.68 and 0.71). On the whole, the analysis shows that the models introduced here could provide local authorities with reliable and precise predictions and alarms about air quality if used on an operational basis.     

Influence of avian reproduction ecotoxicological endpoints in the assessment of plant protection products

The aim of this paper is to examine the statistical relevance of bird species on the endpoints of avian long–term toxicity studies (eggs laid, eggs set, eggs hatching, embryo survivor, 14-day old survivors and eggshell thickness). Data from 561 animals of three different species (Colinus virginianus, Anas platyrynchos and Coturnix coturnix japonica) tested with five different pesticides were analyzed in this study. The substances considered were: Thiamethoxam (EZ-3-(2-chloro-1,3-thiazol-5-ylmethyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene(nitro)amine), Thiacloprid ((Z)-3-(6-chloro-3-pyridylmethyl)-1,3-thiazolidin-2-ylidenecyanamide), Acetamiprid ((E)?N ¹-[(6-chloro-3-pyridyl)methyl]-N ²-cyano-N ¹-methylacetamidine), Phosmet (O,O-dimethyl S-phthalimidomethyl phosphorodithioate) and Dicofol (2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol). Several general lineal mixed models were conducted to evaluate the factors affecting variables used in long-term reproductive toxicity tests. Test significance was p < 0.01 in all models tested. Model R² value was high (0.80) for all variables except for eggs laid (R² = 0.42) for the three species studied. Tukey studentized range test showed significant differences among species and pesticides. For pre-hatching period the differences were significant for eggs laid and eggs set among species. C. japonica showed statistical differences for egg hatching. With respect to embryo survivor and 14 days old survival, significant different were found for C.virginianus and A. platyrynchos, respectively. These results indicate that the selected species have an influence in the endpoints to be used for risk assessment.     

Leaching variations of heavy metals in chelator-assisted phytoextraction by Zea mays L. exposed to acid rainfall

Chelant-enhanced phytoextraction method has been put forward as an effective soil remediation method, whereas the heavy metal leaching could not be ignored. In this study, a cropping-leaching experiment, using soil columns, was applied to study the metal leaching variations during assisted phytoextraction of Cd- and Pb-polluted soils, using seedlings of Zea mays, applying three different chelators (EDTA, EDDS, and rhamnolipid), and artificial rainfall (acid rainfall or normal rainfall). It showed that artificial rainfall, especially artificial acid rain, after chelator application led to the increase of heavy metals in the leaching solution. EDTA increased both Cd and Pb concentrations in the leaching solution, obviously, whereas EDDS and rhamnolipid increased Cd concentration but not Pb. The amount of Cd and Pb decreased as the leaching solution increased, the patterns as well matched LRMs (linear regression models), with R-square (R ²) higher than 90 and 82% for Cd and Pb, respectively. The maximum cumulative Cd and Pb in the leaching solutions were 18.44 and 16.68%, respectively, which was amended by EDTA and acid rainwater (pH 4.5), and followed by EDDS (pH 4.5), EDDS (pH 6.5), rhamnolipid (0.5 g kg⁻¹ soil, pH 4.5), and rhamnolipid (pH 6.5).

     

稻壳活性炭制备及其对磷的吸附

利用农业废弃物稻壳经炭化、活化、酸洗、水洗和干燥等工艺制备出一种富含微孔和中孔结构的稻壳活性炭,其BET比表面积达886.3 m2/g。通过正交实验优化了稻壳活性炭对磷吸附条件,并在该条件下进行了吸附等温和吸附动力学实验研究。结果表明,稻壳活性炭对磷的吸附等温曲线能较好符合Langmuir模型(R2=0.9284)和Freundlich模型(R2=0.9208),由Langmuir线性拟合方程可得稻壳活性炭对磷饱和吸附量达6.93 mg/g;稻壳活性炭对磷的吸附过程可用准二级动力学方程描述(R2=0.9968),吸附速度较快,颗粒内扩散为该过程控速阶段。稻壳活性炭作为一种易得、廉价、高效的填料,在农村分散型污水生态处理技术中,具有良好的应用前景。     

Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether (, E_a/R=580 (±560) K), n-butyl acetate ( (±0.4)×10⁹ M⁻¹ s⁻¹, E_a/R=1000 (±200) K), acetone ( (±0.05)×10⁹ M⁻¹ s⁻¹, E_a/R=1400 (±500) K), methyl ethyl ketone (, E_a/R=1200 (±200) K), methyl iso-butyl ketone (, E_a/R=1200 (±300) K) and methylglyoxal (, E_a/R=1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.     

Comparison of the Photodegradation of Imazethapyr in Aqueous Solution,on Epicuticular Waxes,and on Intact Corn (Zea Mays) and Soybean (Glycine Max) Leaves

A direct, controlled comparison of the photodegradation of imazethapyr has been made between imazethapyr in aqueous solutions, imazethapyr on the surface of epicuticular waxes of corn and soybean plants, and imazethapyr on the surface of intact corn and soybean plant leaves. In some experiments, the imazethapyr solutions were allowed to evaporate partially or fully after application to better model environmental conditions. The photodegradation of imazethapyr was fastest in aqueous solutions (k?=?0.16?±?0.02?h^?1) and slowest on the surface of corn and soybean plants (k_corn?=?0.00048?±?0.001?h^?1 and k_soy?=?0.00054?±?0.003?h^?1). Experiments allowing evaporation during irradiation have intermediate rate constants (e.g., k_corn?=?0.082?±?0.005?h^?1). Finally, identification of photoproducts was also examined on epicuticular waxes of corn and soybean plants for the first time.     

Protection from wintertime rainfall reduces nutrient losses and greenhouse gas emissions during the decomposition of poultry and horse manure-based amendments

Manure-based soil amendments (herein “amendments”) are important fertility sources, but differences among amendment types and management can significantly affect their nutrient value and environmental impacts. A 6-month in situ decomposition experiment was conducted to determine how protection from wintertime rainfall affected nutrient losses and greenhouse gas (GHG) emissions in poultry (broiler chicken and turkey) and horse amendments. Changes in total nutrient concentration were measured every 3 months, changes in ammonium (NH₄⁺) and nitrate (NO₃^?) concentrations every month, and GHG emissions of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) every 7–14 days. Poultry amendments maintained higher nutrient concentrations (except for K), higher emissions of CO₂ and N₂O, and lower CH₄ emissions than horse amendments. Exposing amendments to rainfall increased total N and NH₄⁺ losses in poultry amendments, P losses in turkey and horse amendments, and K losses and cumulative N₂O emissions for all amendments. However, it did not affect CO₂ or CH₄ emissions. Overall, rainfall exposure would decrease total N inputs by 37% (horse), 59% (broiler chicken), or 74% (turkey) for a given application rate (wet weight basis) after 6 months of decomposition, with similar losses for NH₄⁺ (69–96%), P (41–73%), and K (91–97%). This study confirms the benefits of facilities protected from rainfall to reduce nutrient losses and GHG emissions during amendment decomposition.

Implications: The impact of rainfall protection on nutrient losses and GHG emissions was monitored during the decomposition of broiler chicken, turkey, and horse manure-based soil amendments. Amendments exposed to rainfall had large ammonium and potassium losses, resulting in a 37–74% decrease in N inputs when compared with amendments protected from rainfall. Nitrous oxide emissions were also higher with rainfall exposure, although it had no effect on carbon dioxide and methane emissions. Overall, this work highlights the benefits of rainfall protection during amendment decomposition to reduce nutrient losses and GHG emissions.     

Kinetics of phenol biodegradation at high concentration by a metabolically versatile isolated yeast Candida tropicalis PHB5

A highly tolerant phenol-degrading yeast strain PHB5 was isolated from wastewater effluent of a coke oven plant and identified as Candida tropicalis based on phylogenetic analysis. Biodegradation experiments with C. tropicalis PHB5 showed that the strain was able to utilize 99.4 % of 2,400 mg l^?1 phenol as sole source of carbon and energy within 48 h. Strain PHB5 was also observed to grow on 18 various aromatic hydrocarbons. Haldane model was used to fit the exponential growth data and the following kinetic parameters were obtained: μ _max?=?0.3407 h^?1, K _S?=?15.81 mg l^?1, K _i?=?169.0 mg l^?1 (R ²?=?0.9886). The true specific growth rate, calculated from μ _max, was 0.2113. A volumetric phenol degradation rate (V _max) was calculated by fitting the phenol consumption data with Gompertz model and specific degradation rate (q) was calculated from V _max. The q values were fitted with Haldane model, yielding following parameters: q _max?=?0.2766 g g^?1 h^?1, K _S ′?=?2.819 mg l^?1, K _i ′?=?2,093 (R ²?=?0.8176). The yield factor (Y _X/S ) varied between 0.185 to 0.96 g g^?1 for different initial phenol concentrations. Phenol degradation by the strain proceeded through a pathway involving production of intermediates such as catechol and cis,cis-muconic acid which were identified by enzymatic assays and HPLC analysis.     

活性炭-微波辐照处理丁腈胶乳生产废水的研究

以活性炭-微波辐照工艺处理丁腈胶乳生产废水,考察了催化剂的种类及用量、废水初始浓度、废水初始pH值、微波辐照时间和微波功率等对废水COD去除率的影响.结果表明,采用3 g粉末活性炭处理100 mL COD浓度为3500 mg/L左右的丁腈胶乳废水,在微波辐照功率为200 W,辐照时间4 min的条件下,废水COD去除率最高可达96.6%.动力学研究表明,在最佳操作条件下的反应表观过程近似符合一级反应规律,动力学方程为In(C0/C)=0.6034t 0.9247(R=0.9926),反应速率常数k=0.6034 min-1,半衰期t1/2=1.15 min.     

响应面分析法优化稀土废水MAP沉淀法脱氮

经过预处理后的稀土生产废水，其氨氮浓度大幅降低，但并未达到中华人民共和国《稀土工业污染物排放标准》（GB26451-2011）中氨氮浓度限值。实验通过响应面分析法中的Box-Behnken实验设计（BBD），取pH、n（Mg）：n（N）、n（P）：n（N）3因素，采用Design-Expert 8.0.6，建立合适的剩余氨氮浓度及剩余总磷浓度模型，得到回归方程，并分析模型各项指标，各因素及其相互作用对剩余氨氮浓度及剩余总磷浓度的影响。利用预测模型预测最佳实验条件，在最佳实验条件下验证预测结果，并对沉淀物进行X射线衍射（XRD）分析。结果显示，二次响应模型适用于剩余氨氮浓度及剩余总磷浓度，2个模型均拥有较好的拟合程度、可信度及精密度，最优反应条件为：pH=9.88、n（Mg）：n（N）=1.50：1、n（P）：n（N）=1.38：1时，剩余氨氮浓度为46.58 mg/L，剩余总磷浓度为7.85 mg/L。在最优条件下所得到的沉淀物并非纯净的MgNH₄PO₄·6H₂O，还有Mg₃（PO₄）₂·22H₂O生成。     

Evaluation of the mobility of c14‐labelled pesticides in soils by thin layer chromatography using a linear analyser

Abstract

The mobility of seven pesticides in a chromic cambisol soil was studied by soil thin layer chromatography. Pesticide mobilities were determined by means of conventional autoradiographs of the chromatograms, as well as from sequential series of curves and images of the pesticide spots provided by a linear analyser. The R _f values obtained from the autoradiographs and those provided by the linear analyser were quite consistent. Based on such values, pesticide mobility decreased in the following order: acephate > fluometuron > atrazine > ethofumesate > metolachlor > diazinon > glyphosate. According to the mobility scale proposed by Helling and Turner (1968), acephate is highly mobile; atrazine, fluometuron, ethofumesate and metolachlor are moderately mobile; diazinon is slightly mobile; and glyphosate is immobile. The images provided by the linear analyser allow to determine the R _f values for the zones of maximum activity in the pesticide spots (R _f ^max), as well as the activities of different spot zones and those corresponding to R _f and R _f ^max. The results obtained show the image analyser to provide more expeditious R _f measurements from the chromatograms and open up new prospects for using soil TLC to investigate pesticide mobility.     

Uncertainty analysis of developed ANN and ANFIS models in prediction of carbon monoxide daily concentration

This study aims to predict daily carbon monoxide (CO) concentration in the atmosphere of Tehran by means of developed artificial neural network (ANN) and adaptive neuro-fuzzy inference system (ANFIS) models. Forward selection (FS) and Gamma test (GT) methods are used for selecting input variables and developing hybrid models with ANN and ANFIS. From 12 input candidates, 7 and 9 variables are selected using FS and GT, respectively. Evaluation of developed hybrid models and its comparison with ANN and ANFIS models fed with all input variables shows that both FS and GT techniques reduce not only the output error, but also computational cost due to less inputs. FS–ANN and FS–ANFIS models are selected as the best models considering R², mean absolute error and also developed discrepancy ratio statistics. It is also shown that these two models are superior in predicting pollution episodes. Finally, uncertainty analysis based on Monte-Carlo simulation is carried out for FS–ANN and FS–ANFIS models which shows that FS–ANN model has less uncertainty; i.e. it is the best model which forecasts satisfactorily the trends in daily CO concentration levels.     

Aqueous phase methylation as a potential source of methylmercury in wet deposition

The source of monomethylmercury (MMHg) in wet deposition is unknown. Volatilization of gaseous MMHg, evasion and demethylation of dimethylmercury, and methylation of Hg⁰ have been either proposed or tested unsuccessfully as potential sources. Here, we show that MMHg in precipitation, sampled across a wide geographical range in North America, is related positively to an operationally defined and measured reactive Hg species (Hg_R), but connected weakly to total Hg. The mean molar ratio of MMHg:Hg_R measured in continental precipitation (0.025±0.006) is comparable to the MMHg:Hg(II) ratio estimated from first-order rate constants for acetate-mediated Hg methylation and MMHg photolysis (0.025±0.002). This suggests MMHg may be formed in the atmosphere through a reaction between labile Hg(II) complexes and an unknown methylating agent(s), potentially acetate or similar molecules. Availability of Hg(II) appears to limit the reaction, and accordingly, increased atmospheric loadings of Hg could lead to enhanced MMHg in precipitation.     

Modelling of silica diffusion experiments with Si in Boom Clay

A mathematical model describing the dissolution of nuclear glass directly disposed in clay combines a first-order dissolution rate law with the diffusion of dissolved silica in clay. According to this model, the main parameters describing the long-term dissolution of the glass are ηR, the product of the diffusion accessible porosity η and the retardation factor R, and the apparent diffusion coefficient D_app of dissolved silica in clay.For determining the migration parameters needed for long-term predictions, four Through-Diffusion (T-D) experiments and one percolation test have been performed on undisturbed clay cores. In the Through-Diffusion experiments, the concentration decrease after injection of ³²Si (radioactive labelled silica) was measured in the inlet compartment. At the end of the T-D experiments, the clay cores were cut in thin slices and the activity of labelled silica in each slice was determined. The measured activity profiles for these four clay cores are well reproducible.Since no labelled silica could be detected in the outlet compartments, the Through-Diffusion experiments are fitted by two In-Diffusion models: one model assuming linear and reversible sorption equilibrium and a second model taking into account sorption kinetics. Although the kinetic model provides better fits, due to the sufficiently long duration of the experiments, both models give approximately similar values for the fit parameters. The single percolation test leads to an apparent diffusion coefficient value about two to three times lower than those of the Through-Diffusion tests.Therefore, dissolved silica appears to be strongly retarded in Boom Clay. A retardation factor R between 100 and 300 was determined. The corresponding in situ distribution coefficient K_d is in the range 25–75 cm³ g⁻¹. The apparent diffusion coefficient of dissolved silica in Boom Clay is estimated between 2×10⁻¹³ and 7×10⁻¹³ m² s⁻¹. The pore diffusion coefficient is in the range from 6×10⁻¹¹ to 1×10⁻¹⁰ m² s⁻¹.