Relationship between water solubility of organic chemicals and their bioaccumulation by the alga

This paper reports the bioaccumulation of 34 organic chemicals in and on the green alga and their relationship to water solubility.     

The inportance of organic and elemental carbon in the fine atmospheric aerosol particles

During a field campaign the chemical character of fine (d<2.5 μm) aerosol particles was studied at K-puszta, Hungary within the framework of a project of the European Union. The organic and elemental carbon fraction, as well as the concentration of major inorganic constituents with respect to the total fine aerosol mass are presented in this paper. It was found that organic compounds constituted a significant fraction of the total fine aerosol mass, their contribution is comparable to or larger than that of the major water soluble ions. The diurnal variation of aerosol composition was also studied. It can be concluded that the relative abundance of the major constituents is practically the same during the day and at night. The samples were also classified and studied according to the air mass history. It is stated that the aerosol can be separated into two populations with different regression lines between organic and elemental carbon.     

Chemical features and seasonal variation of fine aerosol water-soluble organic compounds in the Po Valley,Italy

We present here an investigation on the annual cycle of the carbonaceous fraction of the Po Valley (Italy) fine (d<1.5 μm) aerosol. Water-soluble organic compounds (WSOC) characterisation was accomplished using a simplified procedure, described in the paper, of a previously proposed methodology. The new simplified procedure allows the analysis of large sets of samples, which was difficult to achieve with the previous complex and labour-intensive method. The results of this study show that the aerosol total carbon (TC) concentration follows the same annual trend as the aerosol inorganic ion constituents, characterised by lower concentration values during the summer and higher concentrations in winter. The total aerosol organic carbon (OC) represents from 90 to 97% of TC, the rest being accounted for by elemental carbon. Within this study, we studied in particular the aerosol WSOC, a class of chemical compounds for which present knowledge is rather limited. In our samples, WSOC account for between 38% (in winter) and 50% (in summer) of OC, in terms of carbon. WSOC were fractionated into three main classes: (a) neutral/basic compounds; (b) mono- and di-carboxylic acids; (c) polyacidic compounds. The three fractions together accounted for an average 87% of total aerosol WSOC. The acidic compounds (mono- and di-carboxylic acids+polyacidic compounds) were found to be far more abundant than the neutral ones in all seasons, with polycarboxylic acids being the most abundant class of WSOC in spring, fall, and winter, while the mono/di-acids are dominant in summer. The main structural features of aerosol WSOC, revealed by proton nuclear magnetic resonance, suggest that WSOC are composed of highly oxidised species with residual aromatic nuclei and aliphatic chains. In particular, neutral compounds are mainly polyols or polyethers, mono/di-acids are mainly hydroxylated aliphatic acidic compounds, and polyacids are highly unsaturated compounds of predominantly aliphatic character, with a minor content of hydroxy groups.     

成都市夏季大气挥发性有机物污染及其对二次有机气溶胶生成的贡献

于2014年7月8日至8月13日在成都市城区和工业区选取两个点位开展挥发性有机物(VOCs)样品采集工作,分析结果显示,成都市夏季城区大气中VOCs质量浓度在34.1~458.8μg/m3,平均值为(137.3±91.8)μg/m3;工业区大气中VOCs质量浓度在26.7~474.9μg/m3,平均值为(135.9±103.5)μg/m3。早高峰时段(7:00~10:00)两个点位VOCs的浓度水平均高于其他时段,说明VOCs浓度受机动车排放的影响较为明显。用·OH消耗速率和臭氧生成潜势评估VOCs大气化学反应活性,结果显示,芳香烃和烯烃是影响大气化学反应活性的关键组分。城区和工业区的二次有机气溶胶(SOA)的生成潜势分别为4.859、4.559μg/m3,芳香烃不仅是臭氧生成潜势的关键活性组分,同时也是SOA的重要前体物。     

The composition and sources of PM2.5 organic aerosol in two urban areas of Chile

Fine particle (PM_2.5) samples were collected, using a charcoal diffusion denuder, in two urban areas of Chile, Santiago and Temuco, during the winter and spring season of 1998. Molecular markers of the organic aerosol were determined using GC/MS. Diagnostic ratios and molecular tracers were used to investigate the origin of carbonaceous aerosols. As main sources, road and non-road engine emissions in Santiago, and wood burning in Temuco were identified. Cluster analysis was used to compare the chemical characteristics of carbonaceous aerosols between the two urban environments. Distinct differences between Santiago and Temuco samples were observed. High concentrations of isoprenoid (30–69 ng m⁻³) and unresolved complex mixture (UCM) of hydrocarbons (839–1369 ng m⁻³) were found in Santiago. High concentrations of polynuclear aromatic hydrocarbons (751±304 ng m⁻³) and their oxygenated derivatives (4±2 ng m⁻³), and of n-alk-1-enes (16±13 ng m⁻³) were observed in Temuco.     

Characterization of fine primary biogenic organic aerosol in an urban area in the northeastern United States

Scanning electron microscopy coupled to energy-dispersive x-ray spectroscopy (SEM/EDX) was used to quantify individual bioparticles in PM_2.5 samples collected during the Pittsburgh Air Quality Study. Microscopy-based estimates of primary biogenic organic aerosol (PBOA) mass were compared to carbohydrate mass associated with PM_2.5. Carbohydrates show substantial seasonal variations, with higher concentrations in the spring and the fall. During the summer, carbohydrates were about 30% of the estimated PBOA concentrations, but in the winter carbohydrate concentrations often greatly exceeded the PBOA mass estimate. Spores and insect detritus were the most abundant PBOA types in the summer samples, while winter samples were comprised predominantly of a mixture of microorganisms, insect and vegetative detritus. During the summer PBOA contributed on average 6.9 ± 5.4% by mass of the PM_2.5 versus 3.3 ± 1.4% of the PM_2.5 mass during the winter.     

Coarse and fine aerosol source apportionment in Rio de Janeiro,Brazil

The metropolitan area of Rio de Janeiro is one of the twenty biggest urban agglomerations in the world, with 11 million inhabitants in the metropolitan area, and has a high population density, with 1700 hab. km^?2. For this aerosol source apportionment study, the atmospheric aerosol sampling was performed at ten sites distributed in different locations of the metropolitan area from September/2003 to December/2005, with sampling during 24 h on a weekly basis. Stacked filter units (SFU) were used to collect fine and coarse aerosol particles with a flow rate of 17 L min^?1. In both size fractions trace elements were analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) as well as water-soluble species by Ion-Chromatography (IC). Also gravimetric analysis and reflectance measurements provided aerosol mass and black carbon concentrations. Very good detection limits for up to 42 species were obtained. Mean annual PM₁₀ mass concentration ranged from 20 to 37 μg m^?3, values that are within the Brazilian air quality standards. Receptor models such as principal factor analysis, cluster analysis and absolute principal factor analysis were applied in order to identify and quantify the aerosol sources. For fine and coarse modes, circa of 100% of the measured mass was quantitatively apportioned to relatively few identified aerosol sources. A very similar and consistent source apportionment was obtained for both fine and coarse modes for all 10 sampling sites. Soil dust is an important component, accounting for 22–72% and for 25–48% of the coarse and fine mass respectively. On the other hand, anthropogenic sources as vehicle traffic and oil combustion represent a relatively high contribution (52–75%) of the fine aerosol mass. The joint use of ICP-MS and IC analysis of species in aerosols has proven to be reliable and feasible for the analysis of large amount of samples, and the coupling with receptor models provided an excellent method for quantitative aerosol source apportionment in large urban areas.     

Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples

The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.     

Secondary organic aerosol formation from cyclohexene ozonolysis in the presence of water vapor and dissolved salts

A series of 90 experiments were conducted in the UC Riverside/CE-CERT environmental chamber to evaluate the impact of water vapor and dissolved salts on secondary organic aerosol formation for cyclohexene ozonolysis. Water vapor (low – 30 ± 2% RH, medium – 46 ± 2% RH, high – 63 ± 2% RH) was found to directly participate in the atmospheric chemistry altering the composition of the condensing species, thus increasing total organic aerosol formation by ～22% as compared to the system under dry (<0.1% RH) conditions. Hygroscopicity measurements also indicate that the organic aerosol composition is altered in the presence of gaseous water. These results are consistent with water vapor reacting with the crigee intermediate in the gas phase resulting in increased aldehyde formation. The addition of dissolved salts ((NH₄)₂SO₄, NH₄HSO₄, CaCl₂, NaCl) had minimal effect; only the (NH₄)₂SO₄ and NaCl were found to significantly impact the system with ～10% increase in total organic aerosol formation. These results indicate that the organics may be partitioning to an outer organic shell as opposed to into the aqueous salt. Hygroscopicity measurements indicate that the addition of salts does not alter the aerosol composition for the dry or water vapor system.     

农村不同类型有机固体废弃物混合堆肥配比优化

为寻求3种农村有机固体废弃物(农村污泥、人粪便、生活垃圾)的最适堆肥配比组合,采用混料设计,分别进行了14组堆肥实验,以WSC/WSN(溶解性碳氮比)、WSCorg(溶解性有机碳)、T(终点C/N与初始C/N的比值)、k(有机质降解速率)作为混合堆肥腐熟程度的判别指标进行响应面分析。结果表明：将三者进行混合堆肥,可有效解决它们单独堆肥时存在的溶解性碳素过高和堆肥进程较慢的问题。堆肥效果相对较优的配比组合（干重比）为生活垃圾27%～45%、人粪便38%～70%和农村污泥0%～27%。在该区间内,堆肥产品WSCorg、WSC/WSN、T和k分别为7.57～8.78?mg·g-1、4.97～6.07、0.43～0.48、0.10～0.12?d-1,达到腐熟标准。     

Characterization of organic aerosol in Big Bend National Park,Texas

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study was conducted in Big Bend National Park, Texas, July through October 1999. Daily PM_2.5 organic aerosol samples were collected on pre-fired quartz fiber filters. Daily concentrations were too low for detailed organic analysis by gas chromatography-mass spectrometry (GC-MS) and were grouped based on their air mass trajectories. A total of 12 composites, each containing 3–10 daily samples, were analyzed. Alkane carbon preference indices suggest primary biogenic emissions were small contributors to primary PM_2.5 organic matter (OM) during the first 3 months, while in October air masses advecting from the north and south were more strongly influenced by biogenic sources. A series of trace organic compounds previously shown to serve as particle phase tracers for various carbonaceous aerosol source types were examined. Molecular tracer species were generally at or below detection limits, except for the wood smoke tracer levoglucosan in one composite, so maximum possible source influences were calculated using the detection limit as an upper bound to the tracer concentration. Wood smoke was found not to contribute significantly to PM_2.5 OM, with contributions for most samples at <1% of the total organic particulate matter. Vehicular exhaust also appeared to make only minor contributions, with maximum possible influences calculated to be 1–4% of PM_2.5 OM. Several factors indicate that secondary organic aerosol formation was important throughout the study, and may have significantly altered the molecular composition of the aerosol during transport.     

Relationship between water solubility of chlorobenzenes and their effects on a freshwater green alga

The effective concentrations of benzene and 12 chlorobenzenes that reduced 50% of the primary productivity (EC₅₀) of a freshwater green alga, $\text{Ankistrodesmus falcatus}$, were determined. Benzene was the least toxic chemical and the toxicity increased as the degree of chlorine substitution in the aromatic ring increased. No EC₅₀ value could be obtained for HCB. A quantitative relationship was found to exist between water solubility, lipophilicity and the EC₅₀. A good correlation was also observed between the EC₅₀ for this alga and other toxicity data for various aquatic biota.     

On the relation between the size and chemical composition of aerosol particles and their optical properties

The light scattering and absorption coefficients of fine atmospheric aerosol particles were recorded in Hungary under rural conditions in 1998–1999 by an integrating nephelometer and particle soot absorption photometer, respectively. In some cases optical properties in the fine size range were compared to those in the coarse particles. Results obtained indicate, as expected, that fine particles control the scattering and absorption caused by the aerosol. In 1999 the size distribution of aerosol particles was also monitored by means of an electric low pressure impactor (ELPI). This makes it possible the study of the relationship between the number, surface and mass concentration in the size range of 0.1–1.0 μm and the optical characteristics by also considering the chemical composition of the particles.     

Mineral constituents in Leccinum scabrum from lowland locations in the central Europe and their relation to concentration in forest topsoil

Leccinum scabrum is an edible mushroom common in European regions in the northern hemisphere. Macro and trace mineral constituents such as Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, P, Rb, Sr and Zn were studied in L. scabrum and in the top soil collected from the same location underneath soil substratum. The “pseudo-total” and labile (extractable fraction of minerals) were measured to get insight into the levels, distribution between the morphological parts of fruiting bodies, potential for their bioconcentration by mushroom and evaluated for human exposure via consumption of the mushroom. The sampling sites include the Dar?lubska Wilderness, Trójmiejski Landscape Park, Sobieszewo Island, Wdzydze Landscape Park and outskirts of the K?trzyn town in Mazury from the norther part of Poland. Median values of K, Rb and P concentrations in dehydrated L. scabrum were for caps in range 27,000–44,000 mg kg^?1, 90–320 mg kg^?1 and 6,200–9,100 mg kg^?1, and followed by Mg at 880–1,000 mg kg^?1, Ca at 48–210 mg kg^?1 and Al at 15–120 mg kg^?1. The median concentrations of Cu, Fe, Mn and Zn in caps were in range 15–27 mg kg^?1 db 38–140 mg kg^?1, 5.3–27 mg kg^?1 and 130–270 mg kg^?1. For Ba and Sr, concentrations on the average were at ～1 mg kg^?1, and almost equally distributed between the caps and stipes of the fruiting bodies. L. scabrum mushrooms were low in toxic Ag, Cd, Hg and Pb, for which the median values in dried caps from five locations were, respectively, in range 0.48–0.98 mg kg^?1 (cap to stipe index, Q_C/S, was 2.5–4.1), 1.0–5.8 mg kg^?1 (Q_C/S 2.9–3.8), 0.36–0.59 mg kg^?1 (Q_C/S 1.6–2.7) and 0.20–0.91 mg kg^?1 (Q_C/S 1.2–1.9). Substantial variations in the concentrations of the “pseudo-total” fraction (extracted by aqua regia) or labile fraction (extracted by 20% solution of nitric acid) of the elements determined in forest topsoils were noted between some of the locations examined. The elements K, P, Cd, Cu, Hg, Mn, Na, Rb and Zn can be considered as those which were bioconcentrated by L. scabrum in fruiting bodies, while the rates of accumulation varied with the sampling location.     

Effect of fluoride on pH, organic matter and solubility of elements in soils

The effect of NaF addition on pH, organic matter and the solubilities of fifteen elements was investigated on twenty-eight surface soil samples. Four concentrations of NaF were added: 0, 10(-2.7), 10(-1.7) and 10(-1.0)m F in solution. Addition of NaF increased the pH and the solubility of organic matter for all soils. The magnitude of these increases was higher for acid than for alkaline soils. Aluminum, Fe and Ca showed the greatest increases in solubility while Mg, K, Mn and P showed intermediate increases. The elements Cd, Cr, Ni, Cu, Zn, B, Mo and Ba showed only slight increases in solubility. Another experiment was conducted to test whether the effects of NaF on pH, organic matter and the solubilities of various elements were due to F or Na. Four levels of NaCl similar to those for NaF were added to three acid and two alkaline soils. The results confirmed the effects of F on soil pH, organic matter and the solubilities of all elements investigated except those of K, Ca and Mg. Addition of Na as NaF resulted in release of K, Ca and Mg from the exchange sites on solid surfaces into solution.     

Appraisal of measurement methods, chemical composition and sources of fine atmospheric particles over six different areas of Northern Belgium

Daily and seasonal variation in the total elemental, organic carbon (OC) and elemental carbon (EC) content and mass of PM_2.5 were studied at industrial, urban, suburban and agricultural/rural areas. Continuous (optical Dustscan, standard tapered element oscillating micro-balance (TEOM), TEOM with filter dynamics measurement system), semi-continuous (Partisol filter-sampling) and non-continuous (Dekati-impactor sampling and gravimetry) methods of PM_2.5 mass monitoring were critically evaluated. The average elemental fraction accounted for 2-6% of the PM_2.5 mass measured by gravimetry. Metals, like K, Mn, Fe, Cu, Zn and Pb were strongly inter-correlated, also frequently with non-metallic elements (P, S, Cl and/or Br) and EC/OC. A high OC/EC ratio (2-9) was generally observed. The total carbon content of PM_2.5 ranged between 3 and 77% (averages: 12-32%), peaking near industrial/heavy trafficked sites. Principal component analysis identified heavy oil burning, ferrous/non-ferrous industry and vehicular emissions as the main sources of metal pollution.     

Chemical characterization of emissions from vegetable oil processing and their contribution to aerosol mass using the organic molecular markers approach

The organic fraction of aerosol emitted from a vegetable oil processing plant was studied to investigate the contribution of emissions to ambient particles in the surrounding area. Solvent-soluble particulate organic compounds emitted from the plant accounted for 10% of total suspended particles. This percentage was lower in the receptor sites (less than 6% of total aerosol mass). Nonpolar, moderate polar, polar, and acidic compounds were detected in both emitted and ambient aerosol samples. The processing and combustion of olive pits yielded a source with strong biogenic characteristics, such as the high values of the carbon preference index (CPI) for all compound classes. Polycyclic aromatic hydrocarbons (PAHs) detected in emissions were associated with both olive pits and diesel combustion. The chromatographic profile of dimethylphenanthrenes (DMPs) was characteristic of olive pit combustion. Organic aerosols collected in two receptor sites provided a different pattern. The significant contribution of vehicular emissions was identified by CPI values (approximately 1) of n-alkanes and the presence of the unresolved complex mixture (UCM). In addition, PAH concentration diagnostic ratios indicated that emissions from catalyst and noncatalyst automobiles and heavy trucks were significant. The strong even-to-odd predominance of n-alkanols, n-alkanoic acids, and their salts indicated the contribution of a source with biogenic characteristics. However, the profile of DMPs at receptor sites was similar to that observed for diesel particulates. These differences indicated that the contribution of vegetable oil processing emissions to the atmosphere was negligible.     

北京城区夏季PM2.5及不同组分化学和生物成分分析

为了解北京城区夏季大气颗粒物PM2.5及其不同组分的化学、生物污染特征,于2014年5月末连续采样一个月,采样后超声洗脱并冷冻干燥得到PM2.5颗粒物,在PM2.5颗粒物的基础上制备PM2.5水溶性组分和PM2.5单纯颗粒物,进而对PM2.5颗粒物及另外两种组分样品中的化学及生物成分进行分析测定。结果表明,8种水溶性离子总质量占PM2.5各样品的质量分数依次为67.71%,33.37%,0.09%（依次为PM2.5水溶性组分、PM2.5颗粒物、PM2.5单纯颗粒物,下述数据也按此顺序描述）;16种“酸提”元素总质量占PM2.5各样品的质量分数依次为4.84%,1.86%,0.78%;各样品中内毒素含量分别为0.054 7 EU·mg-1,0.433 3 EU·mg-1,0.041 9 EU·mg-1;PM2.5颗粒物可以检测到细菌16S rDNA、真菌18S rDNA,拷贝量分别为（2.6±1.0）×108个·g-1、（4.3±0.9）×108个·g-1。     

Estimating long-term population exposure to ozone in urban areas of Europe

Tropospheric ozone concentrations regarded as harmful for human health are frequently encountered in Central Europe in summertime. Although ozone formation generally results from precursors transported over long distances, in urban areas local effects, such as reactions due to nearby emission sources, play a major role in determining ozone concentrations. Europe-wide mapping and modeling of population exposure to high ozone concentrations is subject to many uncertainties, because small-scale phenomena in urban areas can significantly change ozone levels from those of the surroundings. Currently the integrated assessment modeling of European ozone control strategies is done utilizing the results of large-scale models intended for estimating the rural background ozone levels. This paper presents an initial study on how much local nitrogen oxide (NOx) concentrations can explain variations between large-scale ozone model results and urban ozone measurements, on one hand, and between urban and nearby rural measurements, on the other. The impact of urban NOx concentrations on ozone levels was derived from chemical equations describing the ozone balance. The study investigated the applicability of the method for improving the accuracy of modeled population exposure, which is needed for efficient control strategy development. The method was tested with NOx and ozone measurements from both urban and rural areas in Switzerland and with the ozone predictions of the large-scale photochemical model currently used in designing Europe-wide control strategies for ground-level ozone. The results suggest that urban NOx levels are a significant explanatory factor in differences between urban and nearby rural ozone concentrations and that the phenomenon could be satisfactorily represented with this kind of method. Further research efforts should comprise testing of the method in more locations and analyzing the performance of more widely applicable ways of deriving the initial parameters.     

Use of modeling to protect,plan, and manage water resources in catchment areas

The degradation of water resources by diffuse pollution, mainly due to nitrate and pesticides, is an important matter for public health. Restoration of the quality of natural water catchments by focusing on their catchment areas is therefore a national priority in France. To consider catchment areas as homogeneous and to expend an equal effort on the entire area inevitably leads to a waste of time and money, and restorative actions may not be as efficient as intended. The variability of the pedological and geological properties of the area is actually an opportunity to invest effort on smaller areas, simply because every action is not equally efficient on every kind of pedological or geological surface. Using this approach, it is possible to invest in a few selected zones that will be efficient in terms of environmental results. The contributive hydraulic areas (CHA) concept is different from that of the catchment area. Because the transport of most of the mobile and persistent pollutants is primarily driven by water circulation, the concept of the CHA is based on the water pathway from the surface of the soil in the catchment area to the well. The method uses a three-dimensional hydrogeological model of surface and groundwater integrated with a geographic information system called Watermodel. The model calculates the contribution (m³/h or %) of each point of the soil to the total flow pumped in a well. Application of this model, partially funded by the Seine Normandy Basin Agency, to the catchment of the Dormelles Well in the Cretaceous chalk aquifer in the Orvanne valley, France (catchment area of 23,000 ha at Dormelles, county 77), shows that 95 % of the water pumped at the Dormelles Well comes from only 26 % of the total surface area of the catchment. Consequently, an action plan to protect the water resource will be targeted at the 93 farmers operating in this source area rather than the total number of farmers (250) across the entire 23,000 ha. Another model, developed from Epiclès© software, permits the calculation of the under-root nitrate concentrations for each field based on soil type, climate, and farming practices. When the Watermodel and Epiclès© are coupled, nitrate transfers from the soil to the catchment and the river can be modeled. In this study, the initial pollution due to the actual farming practices was simulated and we were also able to estimate the efficiency of the agronomic action plan by testing several scenarios and calculating the time needed to reach the target nitrate concentration in the well.