Atmospheric photochemistry and secondary aerosol formation of urban air in Lyon, France

Photochemical aging of volatile organic compounds (VOCs) in the atmosphere is an important source of secondary organic aerosol (SOA). To evaluate the formation potential of SOA at an urban site in Lyon (France), an outdoor experiment using a Potential Aerosol Mass (PAM) oxidation flow reactor (OFR) was conducted throughout entire days during January-February 2017. Diurnal variation of SOA formations and their correlation with OH radical exposure (OHexp), ambient pollutants (VOCs and particulate matters, PM), Relative Humidity (RH), and temperature were explored in this study. Ambient urban air was exposed to high concentration of OH radicals with OHexp in range of (0.2–1.2)×10¹² molecule/(cm³?sec), corresponding to several days to weeks of equivalent atmospheric photochemical aging. The results informed that urban air at Lyon has high potency to contribute to SOA, and these SOA productions were favored from OH radical photochemical oxidation rather than via ozonolysis. Maximum SOA formation (36 µg/m³) was obtained at OHexp of about 7.4 × 10¹¹molecule/(cm³?sec), equivalent to approximately 5 days of atmospheric oxidation. The correlation between SOA formation and ambient environment conditions (RH & temperature, VOCs and PM) was observed. It was the first time to estimate SOA formation potential from ambient air over a long period in urban environment of Lyon.     

Characterization of seawater and aerosol particle surfactants using solid phase extraction and mass spectrometry

Surface-active organic molecules (surfactants) may influence the ability of an aerosol particle to act as a cloud condensation nuclei by reducing its surface tension. One source of organic mass in aerosol particles, which may also contain surfactants, is bubble bursting on the sea surface. In order to directly compare these molecules in the ocean and aerosol particles, we developed a method using multiple solid phase extractions and high resolution mass spectrometry to characterize surface active organic molecules in both. This method has extraction efficiencies greater than 85%, 75%, and 60% for anionic, cationic, and nonionic surfactant standards, respectively. In this study, we demonstrate the presence of three ionic classes of surface active organics in atmospheric aerosol particles and estuarine water from Skidaway Island, GA. With this extraction method, organic molecules from both estuarine water and atmospheric aerosol particles significantly reduced surface tension of pure water (surface tension depression of ~ 18 mN/m) and had high ratios of hydrogen to carbon (H/C) and low ratios of oxygen to carbon (O/C), indicative of surfactants. While previous work has observed a larger fraction of anionic surface active organics in seawater and marine aerosol particles, here we show cationic surface active organics may make up a large fraction of the total surface active molecules in estuarine water (43%–47%).     

Sorption of metals onto natural organic matter as a function of complexation and adsorbent-adsorbate contact mode

The effect of complexing anion and adsorbate-adsorbent contact mode (static equilibrium or dynamic non-equilibrium) on binding and partition of Cu(2+), Cd(2+) and Zn(2+) onto organic matter (exemplified in a low-moor peat) was studied. The study comprised comparative batch and column flow-through sorption experiments on monometallic solutions of Me-Cl and Me-SO(4) salts, at pH 4.0, and sequential fractionation of sorbed metals with respect to binding strength. Both the presence of an anion having complexing properties (Cl(-)) as well as a contact mode was found to quantitatively and qualitatively affect the sorption capacity and binding strength of organic matter (peat) for metal ions. Complexing effect of Cl(-) on metal ions resulted mostly in reduction of metal ability to form strongly bound metal-organic compounds, in accordance with the order of stability constant of complex ions log K: Cd>Zn>Cu. Flow-through (dynamic) contact mode, which is the most appropriate to simulate environmental conditions, appeared to strongly attenuate the complexing effect of chloride ions on Cd and Zn sorption, and significantly enhance sorption capacity also in the absence of complexing ions. For Cd, it was mainly due to the enrichment in the strongly bound "insoluble organic" fraction, while for Zn the quantitative increase of sorption capacity did not alter significantly its partitioning. Neither a quantitative nor qualitative effect of contact mode on Cu binding was observed. Complex and diverse effects of different environmental parameters on metal sorption capacity and binding strength onto organic matter, which strongly influence metal mobility, leads to the conclusion that the correct simulation of these parameters for ecotoxicological testing is crucial for the reliable predicting of metal bioavailability under actual terrestrial environmental conditions.     

有机肥结构特征对污染土壤Cd形态的影响

研究了以污泥和鸡粪为主要来源的两种不同有机肥主要组分和结构特征差异,结合吸附和土壤平衡试验,探讨了各组分对Cd吸附反应特征和土壤Cd形态分布的影响。结果表明:供试污泥有机肥含有较多的羧基,其最大络合量大于鸡厩肥;同时能更有效降低NH4NO3提取态Cd,但因为结合形态相对不稳定,因此导致EDTA提取态Cd有明显增加。而鸡厩有机肥含有更多π键,芳香化和腐熟化程度较高,与Cd吸附更稳定,在降低NH4NO3提取态Cd的同时也能降低EDTA提取态Cd。研究表明有机肥腐殖化、芳香化程度是影响其对重金属污染土壤修复与改良效果的主要因素。     

碳化温度对牛粪铜和锌形态及生态毒性的影响

通过设置不同的热解温度(350,550和750℃)对牛粪废弃物进行碳化处理,并使用光谱技术手段对牛粪炭的微观特点及Cu、Zn赋存形态进行了分析表征,同时结合淋溶和毒性实验探究了热解温度对牛粪炭生态毒性的影响.结果表明,高温碳化明显改善牛粪孔隙结构,使其比表面积从牛粪原料的1.15m²/g提高至牛粪炭的5.51(350℃)~195.90m²/g(750℃).随着热解温度的提高,牛粪炭pH值从8.18(350℃)提高到了10.14(750℃);牛粪炭中Cu、Zn含量则从牛粪原料中的1.22和1.23mg/g分别升高至18.29~35.11和18.58~31.24mg/g.透射电镜-选区衍射以及X射线能谱分析表明,热解处理可使牛粪中Cu、Zn离子分别转化为副黑铜矿(Cu₄O₃)和红锌矿(ZnO)等金属氧化物,从而明显降低了牛粪炭中水溶态、DTPA提取态以及HNO₃-H₂SO₄提取态的Cu、Zn离子浓度;此外,FTIR分析及混合有机酸浸提实验结果也表明,350℃牛粪炭中酚羟基、烷烃基、羧基、酰胺类等有机官能团通过吸附和络合作用固定未完全转化的Cu离子,而升高热解温度会使得这些官能团显著减少、促进Cu离子的完全转化以及无机物与Cu、Zn离子之间稳定金属氧化物化合键的形成.淋溶和生态毒性实验表明,高于550℃的热解温度能够显著降低牛粪炭中Cu、Zn的溶出率以及生态毒性,是高Cu、Zn含量牛粪废弃物无害化处理的一种推荐优选技术.     

Improved atmospheric mercury simulation using updated gas-particle partition and organic aerosol concentrations

The gaseous or particulate forms of divalent mercury (Hg^II) significantly impact the spatial distribution of atmospheric mercury concentration and deposition flux (FLX). In the new nested-grid GEOS-Chem model, we try to modify the Hg^II gas-particle partitioning relationship with synchronous and hourly observations at four sites in China. Observations of gaseous oxidized Hg (GOM), particulate-bound Hg (PBM), and PM_2.5 were used to derive an empirical gas-particle partitioning coefficient as a function of temperature (T) and organic aerosol (OA) concentrations under different relative humidity (RH). Results showed that with increasing RH, the dominant process of Hg^II gas-particle partitioning changed from physical adsorption to chemical desorption. And the dominant factor of Hg^II gas-particle partitioning changed from T to OA concentrations. We thus improved the simulated OA concentration field by introducing intermediate-volatility and semi-volatile organic compounds (I/SVOCs) emission inventory into the model framework and refining the volatile distributions of I/SVOCs according to new filed tests in the recent literatures. Finally, normalized mean biases (NMBs) of monthly gaseous element mercury (GEM), GOM, PBM, WFLX were reduced from −33%–29%, 95%–300%, 64%–261%, 117%–122% to −13%–0%, −20%–80%, −31%–50%, −17%–23%. The improved model explains 69%–98% of the observed atmospheric Hg decrease during 2013–2020 and can serve as a useful tool to evaluate the effectiveness of the Minamata Convention on Mercury.     

Mesoscale variability of organic matter composition in nw adriatic sediments

We investigated the spatial variability of sediment organic matter content and composition in three areas (A, B and C) of the Northwestern Adriatic Sea, subjected to a putative gradient of trophic state ( i.e. , increasing distance from the Po river outflow) in order to determine the appropriate sample size and replication. The analysis of the mesoscale variability was carried out comparing variability on the scale of meters ( i.e. among different deployments) with the variability observed on a scale of several kilometres ( i.e. among different sampling areas). Sediment samples, collected on April 1999, October 1999, April and October 2000, were analysed for chloropigment content (chlorophyll-a and phaeopygments) and protein, carbohydrate and lipid concentrations. Chloropigment, protein, carbohydrate and lipid concentrations were high, indicating that this system shares trophic conditions typical of highly productive environments. All organic matter components displayed a distribution independent from the increasing distance from the Po river outflow and a clear spatial variability, characterised by significant differences among different areas, but not among deployments. Carbohydrates were the biochemical compound displaying the highest spatial variability among the three areas. Chloropigment, protein, carbohydrate and lipid concentrations displayed also significant temporal changes. When spatial and temporal variability were compared, chlorophyll-a, phaeopigment and protein concentrations displayed a higher temporal than spatial variability. Conversely, for carbohydrates and lipids spatial and temporal variability was of the same order of magnitude. Organic matter composition displayed limited changes among areas, but a strong temporal variability. The results from the Adriatic sea suggest that analyses from sediments collected from a single deployment are sufficient for assessing organic matter concentration and composition over areas of several hundreds of square meters. However, for estimating organic matter composition over larger spatial scales ( i.e. miles) the identification of different sampling areas is needed.     

Effect of sulfur and composted manure on SO4-S,P and micronutrient availability in a calcareous saline–sodic soil

A factorial design with different levels of elemental S and cow manure was used to investigate the effects of S and manure on SO₄-S, P and micronutrient availability in a calcareous saline–sodic soil. The results revealed that the recovery of SO₄-S increased significantly (p≤0.05) in all treatments as elemental S increased, particularly when in combination with manure. The interactional effects of S° and manure application rates resulted in a decrease in soil pH of 0.1 to 0.9 units and increases in soil EC from 0.1 to 2.6 dS m^?1 as result of an increase in the number of oxidisers and the oxidation rate of elemental S. Application of S° in combination with manure led to an increase in soil-available-P (0.6–40 mg kg^?1), DTPA-Zn (0.2–3.9 mg kg^?1) and DTPA-Fe (0.1–5.6 mg kg^?1).     

Comparing measured and modelled forest carbon stocks in high-boreal forests of harvest and natural-disturbance origin in Labrador, Canada

Understanding the effects of disturbance regimes on carbon (C) stocks and stock changes is a prerequisite to estimating forest C stocks and fluxes. Live-tree, dead-tree, woody debris (WD), stump, buried wood, organic layer, and mineral soil C stock data were collected from high-boreal black spruce (Picea mariana (Mill.) B.S.P.) stands of harvest and fire origin and compared to values predicted by the Carbon Budget Model of the Canadian Forest Sector (CBM-CFS3); the core model of Canada's National Forest Carbon Monitoring, Accounting and Reporting System. Data comparing the effect of natural and anthropogenic disturbance history on forest C stocks are limited, but needed to evaluate models such as the CBM-CFS3. Results showed that adjustments to the CBM-CFS3 volume-to-biomass conversion and partitioning parameters were required for the non-merchantable and branch C pools to accurately capture live-tree C stocks in the studied black spruce ecosystems. Accuracy of the CBM-CFS3 modelled estimates of dead organic matter and soil C pools was improved relative to regional default parameters by increased snag fall and >10 cm WD base decay rates. The model evaluation process also highlighted the importance of developing a bryophyte module to account for bryophyte C dynamics and the physical burial of woody debris by bryophytes. Modelled mineral soil C estimates were improved by applying a preliminary belowground slow C pool base decay rate optimized for the soil type of the studied sites, Humo-Ferric Podzols.     

“生物有效性测量”与“全沉积物毒性识别评估(TIE)”联用有效识别出沉积物中主要致毒污染物

沉积物中污染物种类繁多,准确判断其中产生生物毒性的主要来源是个难点,本文作者先采用TIE法初步判断出主要致毒污染物为有机物和重金属(毒性描述阶段(相I)),传统的毒性单位分析结果显示Cr、Cu、Ni、Pb和Zn主要致毒重金属,而为氯氰菊酯、氯氟氰菊酯、溴氰菊酯和氟虫腈为主要致毒有机物中(毒性鉴定阶段(相II))。采用4步分级提取法和Tenax提取法分析了重金属和有机物的生物有效性。生物有效性毒性单位分析更加准确地锁定了毒性主要贡献重金属为Zn、Ni和Pb,毒性主要贡献有机物为氯氰菊酯、氯氟氰菊酯和氟虫腈。沉积物的稀释降低了重金属的毒性并使其毒性贡献鉴定变得复杂,生物有效性测量可以有效地提高TIE结果的准确性。
精选自Xiaoyi Yi, Huizhen Li, Ping Ma and Jing You. Identifying the causes of sediment-associated toxicity in urban waterways in South China: Incorporating bioavailabillity-based measurements into whole-sediment toxicity identification evaluation. Environmental Toxicology and Chemistry: Volume 34, Issue 8, pages 1744–1750, August 2015. DOI: 10.1002/etc.2970
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.2970/full