Toxicity of imidazolium- and pyridinium-based ionic liquids and the co-metabolic degradation of N-ethylpyridinium tetrafluoroborate

We examined the effects of the ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF₆], N-ethylpyridinium tetrafluoroborate [EtPy][BF₄], and N-ethylpyridinium trifluoroacetate [EtPy][CF₃COO] on Pseudomonas fluorescens, a ubiquitous soil bacterium. In the presence of 0.5- and 1% of [BMIM][PF₆] or [EtPy][CF₃COO] the growth of bacteria was inhibited, whereas exposing them to 1% [EtPy][BF₄] increased the lag period wherein bacteria adapt to growth conditions before continuing to grow. However, at higher concentrations (5% and 10%), no growth was observed. The inhibitory effects were evident by a decrease in the optical density of the culture, a decline in the consumption of the carbon source, citric acid, and a change in the size of the bacterium. At concentrations below 1%, [EtPy][BF₄] was metabolized by P. fluorescens in the presence of citric acid. Oxidation of the side alkyl-chain of [EtPy][BF₄] caused the accumulation of N-hydroxylethylpyridinium and pyridinium as major degradation products.     

黄菖蒲和狭叶香蒲根系对氮磷的吸收动力学

采用改进的常规耗竭法，研究了黄菖蒲（Iris pseudacorus L.）和狭叶香蒲（Typha angustifolia L.）根系对NH₄⁺、NO₃^-和H₂PO₄^-的吸收特征及差异。结果表明，这2种植物根系对NH₄⁺、NO₃^-和H₂PO₄^-的吸收动力学特征均可采用Michaelis-Menten方程描述。2种植物根系对NH₄⁺、NO₃^-和H₂PO₄^-的亲和力（Km）和最大吸收速率（Vmax）有显著差异。吸收H₂PO₄^-时，黄菖蒲根系具有较高的Vmax值和较低的Km值，说明黄菖蒲具有嗜磷特性，并能够适应广范围浓度的H₂PO₄^-环境，适宜用于污染水体磷的去除；吸收NO₃^-时，狭叶香蒲根系具有较高的Vmax值和较低的Km值，表明狭叶香蒲可用于广范围浓度NO₃^-污染的水体修复；吸收NH₄⁺时，黄菖蒲根系具有较低的Vmax值和Km值，而狭叶香蒲根系具有较高的Vmax值和Km值，说明黄菖蒲适宜用于NH₄⁺污染较轻水体的修复，而在NH₄⁺污染较重水体中宜选用狭叶香蒲作为先锋植物。     

Monthly and annual bias in weekly (NADP/NTN) versus daily (AIRMoN) precipitation chemistry data in the Eastern USA

Previous comparisons of the data from the National Atmospheric Deposition Program, National Trends Network (NTN) against collocated event sampled data and daily sampled data suggest a substantial bias in the concentration of ammonium [NH₄⁺] and concentrations of several base cations, while the comparability of other ion concentrations ranges among the studies. Eight years of collocated data from five NTN and Atmospheric Integrated Research and Monitoring Network (AIRMoN) sites are compared here. Unlike previous analyses, the data from these two data sets were analyzed in the same laboratory using the same analytical methods; therefore, factors that influence concentration differences can be isolated to sampling frequency and sample preservation techniques. For comparison, the relative biases for these data have been calculated using both median value and volume-weighted mean concentrations, following two different approaches in the literature. The results suggest a relative bias of about 10% in [NH₄⁺] (NTN less than AIRMoN), which is smaller than previous estimates that included the influence of inter-laboratory comparisons. The annual relative bias of [H⁺] increases over the analysis period, which results in a larger total relative bias for [H⁺] than found in a previous analysis of AIRMoN and NTN data. When comparing NTN and AIRMoN data on monthly time scales, strong seasonal variations are evident in the relative bias for [H⁺], [NH₄⁺], and [SO₄²⁻]. Large biases in [SO₄²⁻] (NTN greater than AIRMoN) on monthly times scales have not been detected in previous analyses where data for all seasons were considered together.     

Time Trends and Seasonal Variation of the Rainwater Chemical Composition in Spain

Abstract

A multiple regression model was used to describe temporal variations of the concentrations of H⁺, SO₄ ^{2 -}, NO₃ ^- and NH₄ ⁺ in Spanish rainwater. The model included the effects of linear trend, annual cycle, and precipitation quantity simultaneously.

The model fit very well for SO₄ ^{2 -} and NO₃ ^-, with statistical evidence of annual cycle and effect of precipitation quantity for these two ions and for NH₄ ⁺, but not for H⁺. There is no trend for any ion, with the single exception of a decreasing trend for H⁺ in one of the stations used.     

Levels of persistent organic pollutant and their predictors among young adults

Exposure to persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), dichlorodiphenyldichloroethane (p,p′-DDE), and hexachlorobenzene (HCB) continues to be of concern due to their ubiquitous distribution and high persistence. Current toxicant body burden is still a primary concern within the Akwesasne Mohawk Nation since other studies conducted within the community have shown relationships between these POPs and endocrine disruption.In this article we describe the levels of these toxicants in young adults of the Akwesasne Mohawk Nation between the ages of 17 and 21 years of age (mean age 18.1 years), and investigate potential influences of their current body burden. Seventeen congeners in fourteen chromatographic peaks were detected in 50% or more of the individuals sampled (geometric mean [GM] of the sum of these congeners = 0.43 ppb). Congeners 118, 138[+163 + 164] and 153 had the highest rate of detection (?98%) within the Akwesasne young adults. Of the other organochlorines, HCB (GM = 0.04 ppb) and p,p′-DDE (GM = 0.38 ppb) were found in 100% and 99% of the sample respectively.Significantly higher levels of PCBs were found among individuals who were breastfed as infants, were first born, or had consumed local fish within the past year. When compared to levels of p,p′-DDE, HCB, and 13 specific congeners reported by the CDC for youth between the ages of 12 and 19 years, the geometric means of several congeners (CBs 99, 105, 110, and 118) among the Akwesasne were higher than the reported CDC 90th percentile. In contrast, levels of CB 28 in Akwesasne young adults were ∼50% or less than those of the CDC cohort. p,p′-DDE and HCB levels were generally higher in the CDC cohort (GM of 0.516 and 0.065 ppb, respectively for Mohawks vs. 2.51 and 0.123, respectively, for CDC). Concentrations of non-persistent PCBs among this sample of Akwesasne young adults were higher than those reported by the CDC suggesting continued exposure, but lower than those associated with severe contamination.Additional research into the concentration trends of individual PCB congeners within Akwesasne youth and young adults is warranted to further improve our insight into the determinants and influences of organochlorine concentrations within members of the Akwesasne community.     

Vertical distribution of gases and aerosols: The behaviour of ammonia and related components in the lower atmosphere

Vertical concentration profiles for NH₃, HNO₃ and HCl-gas and for NH₄⁺, NO₃⁻, SO²⁻₄, Cl⁻ and Na⁺ aerosol were obtained from a meteorological tower in the central part of the Netherlands. An upward NH₃ flux of 0.12 μgm⁻² s⁻¹ was calculated from the NH₃ profiles and meteorological data. From the HNO₃ profiles a maximum HNO₃ dry deposition velocity of 4 cm s⁻¹ was calculated. Good agreement was found between the measured concentration products [NH₃]_(g) × [HNO₃]_(g) and the theoretical values at temperatures above 0°C and relative humidities below 80%. In other cases, higher NH₃ and/or HNO concentrations in the gas phase were measured than theoretically predicted.     

富含活性氯与Al_(13)水处理药剂对铜氰络合物去除效能

含重金属铜离子与氰离子(CN)的络合物广泛存在于电镀、冶金等工业废水中,是一种较难处理的污染物。富含活性氯和Al13聚合体的水处理药剂(PACC)兼具氧化和絮凝效能,在处理含重金属氰络合物([Cu(CN)3]2-)废水方面具有良好的应用前景。研究PACC与[Cu(CN)3]2-的反应计量学、动力学,考察了pH、反应时间和投药量等影响因素,确定PACC的最佳工作参数。结果表明,PACC可同时实现对CN的氧化和对Cu2+的絮凝,有效去除水中[Cu(CN)3]2-。使用PACC对[Cu(CN)3]2-的无害化处置过程分为2个阶段:CN-首先被氧化成氰酸根(OCN-);然后OCN-被进一步氧化并生成碳酸氢根和氮气,同时所释放的游离态铜离子被絮凝去除。这2个阶段反应的最佳pH分别为11和8,去除1 mol[Cu(CN)3]2-的最佳投药量为9.35 mol Cl2的PACC;在此条件下反应43 min后,其出水中CN-和Cu2+的浓度均达到排放标准(GB21900-2008)要求。     

Photochemical Conversion of NO to NO2 by Hydrocarbons in an Outdoor Chamber

Significant differences occur between results of chamber work conducted outdoors versus work conducted indoors under constant light intensity. Under outdoor conditions at constant [NO_X]_O, lower [HC]o resulted in lower [NO₂]_max and NO₂ dosage during the daylight hours. The percent reduction in [NO₂]_max was a function of the [HC]₀ reduction and the [NO_X]_O level. Under all experimental conditions the 10 hour N0₂ average to maximum N0₂ concentration ratio appeared to be constant at 0.73 during the daylight hours. A regression equation relating [NO_x]_max to [NO_X]_O, [HC]_O, and measures of solar radiation accounted for 92% of the variance in the data. Although there is unavoidable confoundment between [HC]₀ and solar radiation, the HC term in this regression equation can introduce ±20 % change in [N0₂]_max - This variation can be partially offset or enhanced by variations in solar radiation.     

Seasonal variations of acidic air pollutants in Seoul,South Korea

The annular denuder system (ADS) was used to characterize seasonal variations of acidic air pollutants in Seoul, South Korea. Fifty- four 24 h samples were collected over four seasons from October 1996 to September 1997. The annual mean concentrations of HNO₃, HNO₂, SO₂ and NH₃ in the gas phase were 1.09, 4.51, 17.3 and 4.34 μg m^-3, respectively. The annual mean concentrations of PM_2.5(d_p≤2.5 μm in aerodynamic diameter, 50% cutoff), SO^2-₄, NO^-₃ and NH⁺₄ in the particulate phase were 56.9, 8.70, 5.97 and 4.19 μg m^-3, respectively. All chemical species monitored from this study showed statistical seasonal variations. Nitric acid (HNO₃) and ammonia (NH₃) exhibited substantially higher concentrations during the summer, while nitrous acid (HNO₂) and sulfur dioxide(SO₂) were higher during the winter. Concentrations of PM_2.5, SO^2-₄, NO^-₃ and NH⁺₄ in the particulate phase were higher during the winter months. SO^2-₄, NO^-₃ and NH⁺₄ accounted for 26–38% of PM_2.5. High correlations were found among PM_2.5, SO^2-₄, NO^-₃ and NH⁺₄. The mean H⁺ concentration measured only in the fall was 5.19 nmole m^-3.     

Analysis of Hong Kong daily bulk and wet deposition data from 1994 to 1995

Results from a 1-year daily rainwater sampling program, employing both wet and bulk deposition samplers with replicate samples, from 1994 to 1995 in Hong Kong are presented and analysed. Analyte concentrations were found to vary over a wide range of several orders of magnitude, with [H⁺] for example, from 0.16 to 208.9 μeq dm^-3. Diurnal pH values less than 3.83 were measured on five occasions. A significant correlation between pH and lognormal windspeed has been found. This is taken to indicate the minor importance of long-range transport in determining rainwater acidity, since local pollutant emissions accumulate and react under conditions of atmospheric stability in the sub-tropical climate. The H⁺ wet deposition flux onto a polythene surface was 90 meq m^-2 yr^-1 during 1994–1995 at City University. Dry deposition exerts a neutralizing influence upon the acidity from this wet deposition. Although paired t-tests indicated significant differences between the bulk versus wet deposition datasets for cations, but not anions, the dataset means consequently showed such large standard deviations that t-tests indicated no significant differences. In rainwater, the charges from SO^2-₄ and NO^-₃ anions seldom balance the proton charges, implying that they are also derived from solubilization of primary and secondary airborne Ca²⁺, Mg²⁺ and NH⁺₄ particulate matter in rainwater. Use of the [SO^2-₄]/[NO^-₃] ratios in rainwater in fingerprinting pollutant origins has drawbacks, but is generally indicative of a predominantly regional contribution of these secondary pollutants to rainwater. Bulk deposition pH in Hong Kong would be in the region of 4.1 if basic Ca²⁺ compounds alone did not neutralize acidity. The regional rainout pH, inferred after exhaustive below-cloud scavenging, is about 5. The temporal trends in Hong Kong rainwater acidity are blurred.     

Rate constant for the reaction of ozone with diethyl sulfide

The rate constant for the reaction of diethyl sulfide (DES; C₂H₅SC₂H₅) with ozone was determined for the first time, which was (2.77±0.27)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ under a room temperature of (289±1) K. Experiments were conducted under supposedly pseudo-first-order decay conditions, keeping [DES]₀>50[O₃]₀, but having different combinations of [DES]₀ and [O₃]₀. Cyclohexane was added into the reactor to eliminate the effect of OH radicals. The wall decay of ozone and the role of cyclohexane were also discussed in the present work.     

A 3 year study of the aerosol in northwest Saxony (Germany)

Over three years (1993–1995) daily PM-10 aerosol samples were collected at two locations in Saxony, at the rural measurement station Melpitz and at the north-eastern border of Leipzig. By using ion chromatography the water soluble ions Na⁺, NH⁺₄, K⁺, Mg²⁺, Ca²⁺, Cl^-, NO^-₃and SO^2-₄ were analysed daily. Soot was detected by reflectance measurement and gravimetric analysis. Major trends during this period were observed for soot, nitrate, sulphate and calcium. Some components had typical seasonal distributions, e.g. soot, nitrate and sulphate. The rural station Melpitz was influenced more strongly by the power plants at both sides of the Polish border than the urban area of Leipzig-Halle. During inversion periods, maxima of all aerosol components were measured. However, the highest concentrations during inversion periods decreased during the last years at both locations.     

土壤渗滤介质系统去除雨水径流污染物

利用昆明当地的土壤在室内填装一个土柱渗滤系统，使用配水浓度模拟昆明市区雨水径流污染物浓度，进行去除雨水径流污染物的实验研究，考察系统对COD、TN、NH4＋、NO3^-、NO2^-和TP的去除效果。实验结果表明，该土壤渗滤系统对COD平均去除率为82．04％，对TN的平均去除率为22．64％，对NH；平均去除率为94．26％，但是对NO3^-、NO2^-去除效果较差，对TP平均去除率为96．95％；另外，系统长期运行导致下渗速度降低，出水效果反而变好。     

Evaluating Environmental Parameters for Minimum Ammonium Losses during Composting of Trimming Residues

Abstract

A neural fuzzy system was used to investigate the influence of environmental variables (time, aeration, moisture, and particle size) on composting parameters (pH, organic matter [OM], nitrogen [N], ammonium nitrogen [NH₄ ⁺-N] and nitrate nitrogen [NO₃ ^--N]). This was to determine the best composting conditions to ensure the maximum quality on the composts obtained with the minimum ammonium losses. A central composite experimental design was used to obtain the neural fuzzy model for each dependent variable. These models, consisting of the four independent process variables, were found to accurately describe the composting process (the differences between the experimental values and those estimated by using the equations never exceeded 5–10% of the former). Results of the modeling showed that creating a product with acceptable chemical properties (pH, NH₄ ⁺-N and NO₃ ^--N) entails operating at medium moisture content (55%) and medium to high particle size (3–5 cm). Moderate to low aeration (0.2 L air/min · kg) would be the best compromise to compost this residue because of the scant statistical influence of this independent variable.     

Characteristics of precipitation chemistry at Lushan Mountain, East China: 1992–2009

Introduction

Trends in precipitation pH and conductivity during 1992?C2009, and in ionic compositions from January 2007 to June 2009, are reported from Lushan Mountain, one of the highest mountains in mid-east China. Annual mean pH was in the range of 4.35?C5.01 and showed a statistically very significant (P?P?Results and discussions Over the period of study, Lushan Mountain received more rainfall in spring and summer. The pH values varied seasonally with winter minima. The winter multiyear seasonal mean pH was 4.35. The corresponding summer value was 4.88. SO ₄ ^2? and NO ₃ ^? were the main anions, and NH ₄ ⁺ and Ca²⁺ the main cations. The anion to cation ratio was 0.8?C1.0, and that of [SO ₄ ^2? ] to [NO ₃ ^? ] was 2.4-3.0, much lower than that of the 1980s. However, sulfuric acid was still the main acid present. The ratio of [NH ₄ ⁺ ] to [Ca²⁺] was about 1.0, suggesting that these two alkaline substances provided close acid neutralizing capacity. The ratio of [Cl^?] to [Na⁺] was about 0.67, somewhat lower than that of natural precipitation.

Conclusions

Ionic composition varied seasonally and was closely correlated to the amounts of rainfall and pollution. Trajectory analyses showed that the trajectories to Lushan Mountain could be classified in six clusters and trajectories originating from the South Sea and the areas surrounding Lushan Mountain had the greatest impacts on precipitation chemistry.     

The algal toxicity of silver engineered nanoparticles and detoxification by exopolymeric substances

In this study, we report that silver ions (Ag⁺) from the oxidative dissolution of silver engineered nanoparticles (Ag-ENs) determined the EN toxicity to the marine diatom Thalassiosira weissflogii. Most of the Ag-ENs formed non-toxic aggregates (>0.22 μm) in seawater. When the free Ag⁺ concentration ([Ag⁺]_F) was greatly reduced by diafiltration or thiol complexation, no toxicity was observed, even though the Ag-ENs were better dispersed in the presence of thiols with up to 1.08 × 10⁻⁵ M Ag-ENs found in the <0.22 μm fraction, which are orders of magnitude higher than predicted for the natural aquatic environment. The secretion of polysaccharide-rich algal exopolymeric substances (EPS) significantly increased at increasing [Ag⁺]_F. Both dissolved and particulate polysaccharide concentrations were higher for nutrient-limited cells, coinciding with their higher Ag⁺ tolerance, suggesting that EPS may be involved in Ag⁺ detoxification.     

Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.