The effect of resuspension on the fate of total mercury and methyl mercury in a shallow estuarine ecosystem: a mesocosm study

Sediments are the major repository of mercury in estuaries and could be a significant source of Hg to the overlying water column via release from the solid phase during resuspension. There is, however, little information on the effect of resuspension on Hg partitioning and release to the water column. The objective of this study was to determine the effect of resuspension on the cycling of THg and MeHg between the water column and the sediment. Tidal resuspension was simulated using the MEERC STORM facility. The facility can mimic both realistic bottom shear stress and water column turbulence simultaneously. There were three replicates of each resuspension (R) and no resuspension (NR) mesocosms. Two 4-week experiments were conducted in July and October of 2001: experiment 1 without clams and experiment 2 with clams. Both experiments showed that resuspension of muddy sediment introduced significantly higher particulate THg to the water column as TSS increased. The results suggest that THg was mostly bound to sediment particles with very little release during the resuspension events. In contrast, particulate MeHg was significantly lower in the R tanks where sediment particles with poor MeHg were dominant in the water column during the resuspension events. Dissolved THg and MeHg did not change in concert with changes in particulate load, suggesting that the dynamics between dissolved and particulate phases for both THg and MeHg cannot be explained by an equilibrium partitioning.     

Atmospheric chemistry of alkanes

The reactions of the alkanes under atmospheric conditions and in the presence of oxides of nitrogen are reviewed and evaluated. Particular emphasis is placed upon their subsequent reactions after the initial OH radical reaction under conditions where the alkyl peroxy radicals produced react predominantly with NO, rather than with HO₂ and/or RO₂ radicals. Methods are discussed for estimating the overall OH radical rate constants, the number of molecules of NO consumed per alkane molecule reacted, and the products formed and their yields.     

The photo-oxidations of propyl acetates in synthetic air-HONO-NO x mixtures: Product formation studies and proposed kinetic mechanisms

The formation of products following the hydroxyl radical initiated photo-oxidations of n-and isopropyl acetates has been studied. Mixtures of synthetic air containing a few ppm of nitrous acid, nitric oxide, nitrogen dioxide and one of the propyl acetates were irradiated with sunlamps in a Teflon bag smog chamber. The decay of reactants and the formation of products was monitored by chemiluminescent analysis or by gas chromatography. The major primary products from the photo-oxidation of n-propyl acetate are acetaldehyde and propionaldehyde while from isopropyl acetate they are acetone and methyl nitrate. It was not possible to analyse for formaldehyde, an expected primary product in these systems. The nature and distribution of products indicate that a significant fraction of primary products arise from decomposition reactions of the alkoxy-type radicals generated following the initial attack of hydroxyl radicals on the esters. The derived reaction stoichiometries (molecules of NO oxidised per molecule of ester reacted) are also consistent with the proposed mechanisms.     

高温下甲基丙烯酸正丁酯ATRP的合环失活

以2-溴代异丁酸乙酯[2-(E iB)-B r]为引发剂,CuB r/2,2’-bpy为催化体系,进行了甲基丙烯酸正丁酯(n-BMA)在异丙醇(IPA)/水中的原子转移自由基聚合,在16.5~100℃范围内研究了温度对聚合反应活性特征的影响。动力学结果表明,低温时反应有良好可控性,温度升至85℃以上时,聚合反应呈现出一系列非活性特征,聚合进行到一定程度后转化率不再增加,所有的链都成为死链。红外光谱的结果证明,较高温度时处于休眠态的增长链发生了合环反应,导致了增长链的永久失活。     

A Three-Dimensional Simulation of HO x Concentrations Over East Asia During TRACE-P

The Models-3 Community Multi-scale Air Quality modeling system (CMAQ) coupled with the Regional Atmospheric Modeling System (RAMS) is used to simulate three-dimensional concentration distributions of hydroxyl (OH) and hydroperoxyl (HO₂) radicals over the western Pacific Ocean during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) field campaign. Modeled values of OH and HO₂ and their closely related chemical species and photolysis rates are compared with observational data collected onboard the DC-8 aircraft. Comparison shows that the model reasonably reproduced these observed values over a broad range of conditions with an overall tendency to overestimate the measured OH and HO₂ by a factor of 1.56 and 1.24, respectively. A case study of OH, HO₂ and their closely related chemical species and photolysis rates along the DC-8 flights 11 and 12 conducted on 17–18 March 2001 shows that the model reproduces the temporal and spatial variations reasonable well, and produces more reliable OH and HO₂ concentrations in the polluted environment than in the clean marine boundary layer.     

Absolute Rate Coefficients for the Gas-Phase Reactions of NO3 Radical with a Series of Monoterpenes at T = 298 to 433 K

The aim of this work is to study the reactivity of some naturally emitted terpenes, 2-carene, sabinene, myrcene, -phellandrene, d-limonene, terpinolene and -terpinene, towards NO3 radical to evaluate the importance of these reactions in the atmosphere and their atmospheric impact. The experiments with these monoterpenes have been carried out under second-order kinetic conditions over the range of temperature 298–433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). This work is the first temperature dependence study for the reactions of the nitrate radical with the above-mentioned monoterpenes. The measured rate constants at 298 K for the reaction of NO3 with such terpenes are as follows: 2-carene, 16.6 ± 1.8, sabinene 10.7 ± 1.6, myrcene 12.8 ± 1.1, -phellandrene 42 ± 10, d-limonene 9.4 ± 0.9, terpinolene 52 ± 9 and -terpinene 24 ± 7, in units of 10-12 cm3 molecule-1 s-1. The proposed Arrhenius expressions, for the reactions of NO3 with 2-carene, sabinene, myrcene and -phellandrene are, respectively k1 = (1.4 ± 0.7) × 10-12 exp[(741 ± 190/T)] (cm3 molecule-1 s-1), k2=(2.3 ± 1.3) × 10-10 exp[–(940 ± 200/T)] (cm3 molecule-1 s-1), k3 = (2.2 ± 0.2) × 10-12 exp[(523 ± 35/T)] (cm3 molecule1 s-1) and k4 = (1.9 ± 1.3) × 10-9 exp[–(1158 ± 270/T)] (cm3 molecule-1 s-1). A decrease in the rate constants when raising the temperature has also been found for the reaction of d-limonene with NO3 while an increase in the rate constant with temperature has been observed for the reactions of terpinolene and -terpinene with NO3. Tropospheric half-lives for these terpenes have been calculated at night and during the day for typical NO3 and OH concentrations showing that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with NO3 radical can be an important, if not dominant, loss process for these naturally emitted organics and for NO3 radicals.     

Rate constants for reactions of OH radicals with some Br-containing haloalkanes

Rate constants have been measured for the gas-phase reactions of hydroxyl radical with two halons and three of their proposed substitutes and also with CHClBr-CF₃ using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units are 10^–13 cm³ molecule^–1 s^–1): (9.3 _–0.9 ^+1.0 ) exp{–(1326±33)/T} for CHF₂Br; (7.2 _–0.6 ^+0.7 ) exp{–(1111±32)/T} for CHFBrCF₃; (8.5 _–0.8 ^+0.9 ) exp{–(1113±35)/T} for CH₂BrCF₃; (12.8 _–1.2 ^+1.5 ) exp{–(995±38)/T} for CHClBrCF₃. The rate constants at 298 K have been estimated to be <2×10^–17 cm³ molecule^–1 s^–1 for CF₃Br and CF₂Br—CF₂Br. The atmospheric lifetimes due to hydroxyl attack have been estimated to be 5.5, 3.3, 2.8, and 1.2 years for CHF₂Br, CHFBr—CF₃, CH₂Br—CF₃ and CHClBr—CF₃, respectively.     

Determination of rate constants for reactions of some hydrohaloalkanes with OH radicals and their atmospheric lifetimes

Rate constants have been measured for the gas-phase reactions of hydroxyl radical with partly halogenated alkanes using the discharge-flow-EPR technique over the temperature range 298–460 K. The following Arrhenius expressions have been derived (units 10^–13 cm³ molecule^–1 s^–1): (8.1 _–1.2 ^+1.5 ) exp{–(1516±53)/T} for CHF₂Cl (HCFC-22); (10.3 _–1.5 ^+1.8 ) exp{–(1588±52)/T} for CH₂FCF₃ (HFC-134a); (11.3 _–1.6 ^+2.1 ) exp{–(918±52)/T} for CHCl₂CF₂Cl (HCFC-122); (9.2 _–2.0 ^+2.5 ) exp{–(1281±85)/T} for CHFClCF₂Cl (HCFC-123a).The atmospheric lifetimes for the substances have been estimated to be 12.6, 12.9, 1.05, and 4.8 years, respectively, and the accuracy of the estimates is discussed.     

Atmospheric chemistry of the monoterpene reaction products nopinone,camphenilone, and 4-acetyl-1-methylcyclohexene

Rate constants for the gas-phase reactions of OH radicals with nopinone (6,6-dimethylbicyclo[3.1.1]heptan-2-one) and camphenilone (3,3-dimethylbicyclo[2.2.1]heptan-2-one) and for the reactions of 4-acetyl-1-methylcyclohexene with OH and NO₃ radicals and O₃ have been measured at 296±2 K. The rate constants (cm³ molecule^–1 s^–1 units) obtained were, for reaction with the OH radical: nopinone, (1.43±0.37)×10^–11; camphenilone, (5.15±1.44)×10^–12; and 4-acetyl-1-methylcyclohexene, (1.29±0.33)×10^–10; for reaction with the NO₃ radical: 4-acetyl-1-methylcyclohexene, (1.05±0.38)×10^–11; and for reaction with O₃: 4-acetyl-1-methylcyclohexene, (1.50±0.53)×10^–16. These data are used to calculate the tropospheric lifetimes of these monoterpene atmospheric reaction products.