酚类化合物对硝化颗粒污泥活性抑制的定量结构 活性相关研究

测定了酚类化合物对硝化颗粒污泥活性抑制的logIC₅₀值，以量子化学参数为自变量，应用偏最小二乘法（PLS），建立了酚类化合物对硝化颗粒污泥活性抑制的定量结构活性相关（QSAR）模型。模型所提取的PLS主成分所能解释的因变量总方差的比例Q²_cum为0.820，表明模型具有较好的稳定性和预测能力。模型的结果表明，影响酚类化合物对硝化颗粒污泥活性抑制的主要因素是logkow、CCR和E_homo，酚类化合物对硝化颗粒污泥活性抑制的logIC₅₀随着分子logkow的增大而减小，随着E_homo和CCR的增大而增大。     

Determination of the dietary biomagnification of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane with the rainbow trout (Oncorhynchus mykiss)

Separate 77-d fish feeding studies were conducted on the cyclic volatile methylsiloxane (cVMS) chemicals octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane with the rainbow trout, Oncorhynchus mykiss, with the determination of biomagnification factor (BMF) and lipid-adjusted BMF (BMF(L)) values as the final experimental metrics. The studies used fish food concentrations of ∼500 μg g⁻¹ for exposure periods of 35 d, followed by a depuration period of 42 d with clean food. The fish tissue concentrations of D4 and D5 achieved empirical steady-state by day 21 in each study. By day 7 of exposure, total ¹⁴C activity of both compounds had moved from the fish gastrointestinal (GI) tract into surrounding tissue. An absence of significant fish growth during the initial depuration phase allowed for measurement of empirical depuration rate constants (k₂) independent of growth dilution for D4 and D5 of 0.035 and 0.040 d⁻¹, respectively, corresponding to elimination half-lives of approximately 20 d. These rate constants indicated that ∼70–75% of steady-state was achieved during exposure in both studies, resulting in empirical steady-state BMF and BMF(L) values of 0.28 and 0.66 for D4, respectively, and 0.32 and 0.85 for D5, respectively. Kinetic modeling using simple first-order uptake and depuration dynamics produced good agreement with experimental data, with D4 and D5 assimilation efficiencies of 40% and 44%, respectively. Growth-corrected depuration rate constants modeled over the entire study data set indicated slower elimination kinetics for D4 (k₂ of 0.007 d⁻¹ or half-life of 100 d) compared to D5 (k₂ of 0.010 d⁻¹ or elimination half-life of 69 d). Kinetic BMF_k values (i.e., k₁/k₂) for D4 and D5 were 1.7 and 1.3, respectively, with lipid-adjusted BMF_k(L) values of 4.0 and 3.4, respectively.     

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.     

Cation exchange in a glacial till drumlin at a road salt storage facility

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d^− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d^− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k_max = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d^− 1. The stable isotope-based biodegradation rate constant of 0.0027 d^− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d^− 1. With MM-kinetics a maximum degradation rate of k_max = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor ε_field of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.     

Peroxidase-mediated removal of endocrine disrupting compound mixtures from water

Several classes of oxidative enzymes have shown promise for efficient removal of endocrine disrupting compounds (EDCs) that are resistant to conventional wastewater treatments. Although the kinetics of reactions between individual EDCs and selected oxidative enzymes are well documented in the literature, there has been little investigation of reactions with EDC mixtures. This makes it impossible to predict how enzyme-mediated treatment systems will perform since wastewater effluents generally contain multiple EDCs. This paper reports pseudo-first order rate constants for a model oxidative enzyme, horseradish peroxidase (HRP), during single-substrate (k₁) and mixed-substrate (k_1-MIX) reactions. Measured values are compared with literature values of three Michaelis-Menten parameters: half-saturation constant (K_M), enzyme turnover number (k_CAT), and the ratio k_CAT/K_M. Published reports had suggested that each of these could be correlated with HRP reactivity towards EDCs in mixtures, and empirical results from this study show that K_M can be used to predict the sequence of EDC removal reactions within a particular mixture. We also observed that k_1-MIX values were generally greater than k₁ values and that compounds exhibiting greatest estrogenic toxicities reacted most rapidly in a given mixture. Finally, because K_M may be tedious to measure for every EDC of interest, we have constructed a quantitative structure-activity relationship (QSAR) model to predict these values. This model predicts K_M quite accurately (R² = 89%) based on two molecular characteristics: molecular volume and hydration energy. Its accuracy makes this QSAR a useful tool for predicting which EDCs will be removed most efficiently during enzyme treatment of EDC mixtures.     

载钴活性焦对As(V)的吸附性能与去除效果

使用沉淀负载法制备了载钴活性焦,并研究了溶液pH值、反应时间、As(V)初始浓度以及共存阴离子等对载钴活性焦吸附去除水环境中As(V)的影响。结果表明,(1)载钴后活性焦的比表面积和孔容积分别提高了20.87%和43.47%;(2)载钴活性焦对As(V)最佳吸附pH值为4.0,当As(V)的初始浓度为10 mg/L时,As(V)去除率可达97%;(3)吸附过程符合准二级动力学模型(k2=0.66,R2=0.96),吸附等温线为Freundlich型(kF=8.227,1/n=0.396,R2=0.97);(4)稳定性实验验证了载钴活性焦的稳定性,钴不易脱附,最大脱附率仅为0.145%。     

Bioaccumulation and depuration of anthracene in Penaeus monodon (Fibricius) through food ingestion

Understanding on the bioaccumulation and depuration of PAHs (polycyclic aromatic hydrocarbons) in Penaeus monodon is important in seafood safety because it is one of the most popular seafood consumed worldwide. In this study, we used anthracene as the precursor compound for PAHs accumulation and depuration in the shrimp. Commercial feed pellets spiked with anthracene were fed to P. monodon. At 20 mg kg⁻¹ anthracene, P. monodon accumulated 0.1% of the anthracene from the feed. P. monodon deputed the PAH two times faster than its accumulation. The shrimp reduced its feed consumption when anthracene content in the feed exceeded 20 mg kg⁻¹. At 100 mg kg⁻¹ anthracene, P. monodon started to have necrosis tissues on the posterior end of their thorax. The bioaccumulation factor (BAF), uptake rate constant (k₁) and depuration rate constant (k₂) of anthracene in P. monodon were 1.15 × 10⁻³, 6.80 × 10⁻⁴ d⁻¹ and 6.28 × 10⁻¹ d⁻¹, respectively. The depuration rate constant is about thousand times higher than the uptake rate constant and this indicated that this crustacean is efficient in depurating hydrocarbons from their tissue.     

Role of some organic inhibitors on the oxidation of dissolved sulfur dioxide by oxygen in rainwater medium

In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R _o = k _o[S(IV)]], where k _o is the first-order rate constant and R _o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k _obs = k _o/(1 + B [Inh]), where k _obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10^?5 to 1.5?×?10^?4 s^?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?10⁴) (ethanol) and (3.95?±?2.36)?×?10⁴ (2-butanol) at 25 °C.     

Respiratory uptake kinetics of neutral hydrophobic organic chemicals in a marine benthic fish, Pseudopleuronectes yokohamae

We investigated the respiratory uptake kinetics of polychlorinated biphenyls (PCBs), organohalogen pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and 2,2′,4,4′-tetrabrominated diphenyl ether (BDE #47) in a marine benthic fish, Pseudopleuronectes yokohamae. The respiratory uptake efficiencies (E_W) of the chemicals, of which there have been no reports for the majority of persistent organic pollutants (POPs), were obtained by measuring the respiratory uptake rate constants (k₁) and the oxygen consumption rates of fish. Fish were exposed to water in which these chemicals were dissolved at environmentally relevant concentrations for 28 d, followed by 168 d of depuration in clean seawater. The k₁ and E_W values for 99 compounds were obtained, and they ranged from 2000 to 42 000 L kg-lipid⁻¹ d⁻¹ and from 0.060 to 1.3, respectively. The E_W values of the chemicals, except for PAHs, tended to increase with increasing values of the log octanol–water partition coefficients (K_OW) of the chemicals up to a log K_OW of 5. For log K_OW in the range 3–5, the E_W values in this study were much lower than those in a published study (about one-third). As a result of analysis by a two-phase resistance model, the resistance of transport rates to the lipid phase in this study was lower than was the case in the published study. These findings indicate that the E_W predicted by the published study for log K_OW in the range 3–5 may differ among fish species and water temperature, and further study is needed.     

Influence of short-time imidacloprid and acetamiprid application on soil microbial metabolic activity and enzymatic activity

The influence of two neonicotinoids, i.e., imidacloprid (IMI) and acetamiprid (ACE), on soil microbial activities was investigated in a short period of time using a combination of the microcalorimetric approach and enzyme tests. Thermodynamic parameters such as Q _T (J g^?1 soil), ?H _met (kJ mol^?1), J _Q/S (J g^?1 h^?1), k (h^?1), and soil enzymatic activities, dehydrogenase, phosphomonoesterase, arginine deaminase, and urease, were used to evaluate whole metabolic activity changes and acute toxicity following IMI and ACE treatment. Various profiles of thermogenic curves reflect different soil microbial activities. The microbial growth rate constant k, total heat evolution Q _T (expect for IMI), and inhibitory ratio I show linear relationship with the doses of IMI and ACE. Q _T for IMI increases at 0.0–20 μg g^?1 and then decreases at 20–80 μg g^?1, possibly attributing to the presence of tolerant microorganisms. The 50 % inhibitory ratios (IC₅₀) of IMI and ACE are 95.7 and 77.2 μg g^?1, respectively. ACE displays slightly higher toxicity than IMI. Plots of k and Q _T against microbial biomass-C indicate that the k and Q _T are growth yield-dependent. IMI and ACE show 29.6; 40.4 and 23.0; and 23.3, 21.7, and 30.5 % inhibition of dehydrogenase, phosphomonoesterase, and urease activity, respectively. By contrast, the arginine deaminase activity is enhanced by 15.2 and 13.2 % with IMI and ACE, respectively. The parametric indices selected give a quantitative dose-response relationship of both insecticides and indicate that ACE is more toxic than IMI due to their difference in molecular structures.     

Levels of PCDD/Fs,PCBs and PBDEs in breast milk of women living in the vicinity of a hazardous waste incinerator: Assessment of the temporal trend

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in previous surveys carried out in the same area in 1998 (baseline study), 2002 and 2007. The current total concentrations of 2,3,7,8-chlorinated PCDD/Fs in breast milk ranged from 18 to 126 pg g⁻¹ fat (1.1–12.3 pg WHO₂₀₀₅-TEQ_PCDD/F), while the total levels of PCBs ranged from 27 to 405 pg g⁻¹ fat (0.7–5.3 pg WHO₂₀₀₅-TEQ_PCB). In turn, PBDE concentrations (sum of 15 congeners) ranged 0.3–5.1 g g⁻¹ fat, with a mean value of 1.3 ng g⁻¹ fat. A general decrease in the concentrations for PCDD/Fs, both planar and total PCBs, and PBDEs in breast milk was observed. The levels of PCDD/Fs, PCBs, and PBDEs in milk of women living in urban zones were higher than those corresponding to industrial zones (41%, 26%, and 8%, respectively). For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants that we have also observed in recent studies carried out in the same area of study.     

Rate Constants for the Reaction of OH with Halocarbons in the Presence of O2 + N2

Rates of CO₂ production in the reaction CO + OH and CO + OH + halocarbon have been used to determine rate constants for some OH + halocarbon reactions at 29.5°C relative to that of k(CO + OH) = 2.69 × 10^?13 cm³ molecule^?1 sec^?1. The following rate constants were obtained: k(OH + CH₃Cl) = 3.1 ± 0.8, k(OH + CH₂Cl₂) = 2.7 ± 1.0, k(OH + C₂H₅Cl) = 44.0 ± 25, k(OH + CICH₂CH₂CI) = 6.5, (<29) and k(OH + CH₃CCl₃) = 2.1 (<5.7) cm³ molecule^?1 sec^?1 × 10^?14. The k values, CH₂Cl₂ excepted, are in substantial agreement with determinations made in nonoxygen environments. The present results for CH₂Cl₂ are almost certainly in error due to difficulties with the competitive approach used.     

Hg Reactions in the Presence of Chlorine Species: Homogeneous Gas Phase and Heterogeneous Gas-Solid Phase

Abstract

The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (α), overall rate constant (k′ ), and activation energy (E _a), were estimated based on the simple overall reaction pathway. The reaction order with respect to C _Hg, k′, and E _a were found to be 1.55, 5.07 x 10^-2exp(-1939.68/T) [(μg/m³)^-0.55(s)^-1], and 16.13 [kJ/mol], respectively. The effect of chlorine species (HCl, CH₂Cl₂) on the in situ Hg capture method previously de-veloped²⁸ was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface

Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe⁰) is mediated by the thin film of iron (hydr)oxides found on Fe⁰ under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl₄) degradation by Fe⁰ was studied under the influence of various anions, ligands, and initial CCl₄ concentrations ([P]_o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl₄ disappearance (k_CCl4), and zero order for the appearance of dissolved Fe²⁺ (k_Fe²⁺). The rate of dechlorination exhibits saturation kinetics with respect to [P]_o, suggesting that CCl₄ is transformed at a limited number of reactive surface sites. Because oxidation of Fe⁰ by CCl₄ is the major corrosion reaction in these systems, k_Fe²⁺ also approaches a limiting value at high CCl₄ concentrations. The adsorption of borate strongly inhibited reduction of CCl₄, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased k_CCl4 (and k_Fe²⁺). Thus, it appears that the relatively strong complexation of these ligands at the oxide–electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.