Modeling secondary organic aerosol formation from oxidation of α-pinene, β-pinene, and d-limonene

The biogenic species α-pinene, β-pinene, and d-limonene are among the most abundant monoterpenes emitted globally. They are also important precursors to secondary organic aerosol (SOA) formation in the atmosphere. This study involves the development of proposed oxidation mechanisms for these three species. Semi- and non-volatile oxidation products with the potential to lead to SOA formation are predicted explicitly. Simulation code that describes the gas-phase oxidation mechanisms including reactions that lead to ozone (O₃) formation is coupled to an equilibrium absorptive partitioning code. The coupled model is used to simulate both gas-phase chemistry and SOA formation associated with oxidation of these three species in chamber experiments involving single as well as multiple oxidants. For the partitioning model, required molecular properties of the oxidation products are taken from the literature or estimated based on structural characteristics. The predicted O₃ and SOA concentrations are typically within ±50% of measured values for most of the experiments except for the experiments with low initial hydrocarbon concentrations and the nitrate radical experiments with α-pinene. The developed model will be used to update a gas-phase chemical mechanism and a SOA formation module used in a three-dimensional air quality model.     

Detecting points as developmental delay based on the life-history development and urosome deformity of the harpacticoid copepod, Tigriopus japonicus sensu lato, following exposure to benzo(a)pyrene

To identify ecotoxicological responses to an endocrine disrupter, benzo(a)pyrene, we examined the life-history of the harpacticoid copepod, Tigriopus japonicus sensu lato. Based on the life-history of copepods, survival rate of nauplii (NSR) and copepodites (CSR), copepodite emergence day (CED) and adult male emergence day (AMED), sex ratio (MER), brooding success rate (BSR), and first brooding day of adult females (FBD) were measured. Significant differences were observed in the survival and development of nauplii (NSR and CED) and sex ratio (MER) of exposed and non-exposed copepods. Moreover, high concentration of BaP can be lethal to copepodite and exhibited a delay of growth. In this study, the CED and AMED among ecotoxicological response based on life-history developments were delayed and the body characteristics decreased in response to exposure to benzo(a)pyrene. The dwarfism and urosome deformity of the T. japonicus s.l. was exhibited in response to chemical exposure. Specifically, the body characteristics and biomass of dwarf copepods that had been exposed to benzo(a)pyrene were 30% and 50% lower than the control group, respectively. The incidence of abnormal urosomes was divided into two types. The first deformity type was signs of shrinkage in the middle of the urosome or the entire urosome was narrower than those of the control organisms. In the second type, the anal somite and the distal side of the urosome had abnormally swelled. Taken together, the nauplii and copepodid development of T. japonicus s.l. can be used as a useful biomaker for detecting developmental delay based on their entire life-history. In addition, the urosome deformity was used a good potential monitoring tool invading various chemicals and environmental contamination into water system.     

Phytoremediation potential of the novel atrazine tolerant Lolium multiflorum and studies on the mechanisms involved

Atrazine impact on human health and the environment have been extensively studied. Phytoremediation emerged as a low cost, environmental friendly biotechnological solution for atrazine pollution in soil and water. In vitro atrazine tolerance assays were performed and Lolium multiflorum was found as a novel tolerant species, able to germinate and grow in the presence of 1 mg kg⁻¹ of the herbicide. L. multiflorum presented 20% higher atrazine removal capacity than the natural attenuation, with high initial degradation rate in microcosms. The mechanisms involved in atrazine tolerance such as mutation in psbA gene, enzymatic detoxification via P₄₅₀ or chemical hydrolysis through benzoxazinones were evaluated. It was demonstrated that atrazine tolerance is conferred by enhanced enzymatic detoxification via P₄₅₀. Due to its atrazine degradation capacity in soil and its agronomical properties, L. multiflorum is a candidate for designing phytoremediation strategies for atrazine contaminated agricultural soils, especially those involving run-off avoiding.     

C60 fullerene: a powerful antioxidant or a damaging agent? The importance of an in-depth material characterization prior to toxicity assays

Since the discovery of fullerenes in 1985, these carbon nanospheres have attracted attention regarding their physico/chemical properties. Despite little knowledge about their impact on the environment and human health, the production of fullerenes has already reached an industrial scale. However, the toxicity of C₆₀ is still controversially discussed.The aim of this study was to clarify the biological effects of tetrahydrofuran (THF) suspended C₆₀ fullerene in comparison to water stirred C₆₀ fullerene suspensions. Beyond that, we analyzed the effects on the Crustacea Daphnia magna an indicator for ecotoxicological effects and the human lung epithelial cell line A549 as a simplified model for the respiratory tract.We could demonstrate that water-soluble side products which were formed in THF nC₆₀ suspension were responsible for the observed acute toxic effects, whereas fullerenes themselves had no negative effect regardless of the preparative route on either A549 cell in vitro or D. magna in vivo.     

Acute toxicity of 353-nonylphenol and its metabolites for zebrafish embryos

Background, aim and scope  Nonylphenol (NP) can be detected in the aquatic environment all over the world. It is applied as a technical mixture of isomers of which 353-NP is the most relevant both in terms of abundance (about 20% of total mass) and endocrine potential. 353-NP is metabolised in sewage sludge. The aims of the present study were to determine and to compare the acute toxicity of t-NP, 353-NP and its metabolites as well as to discuss if the toxicity of 353-NP changes during degradation. Materials and methods  353-NP and two of its metabolites were synthesised. The zebrafish embryo test was performed according to standard protocols. Several lethal and non-lethal endpoints during embryonal development were reported. NOEL, LOEL and EC₅₀ were calculated. Results  All tested compounds caused lethal as well as non-lethal malformations during embryo development. 353-NP showed a higher toxicity (EC₅₀ for lethal endpoints 6.7 mg/L) compared to its metabolites 4-(3.5-dimethyl-3-heptyl)-2-nitrophenol (EC₅₀ 13.3 mg/L) and 4-(3,5-dimethyl-3-heptyl)-2-bromophenol (EC₅₀ 27.1 mg/L). Discussion  In surface water, concentrations of NP are far below the NOEC identified by the zebrafish embryo test. However, in soils and sewage sludge, concentrations may reach or even exceed these concentrations. Therefore, sludge-treated sites close to surface waters should be analysed for NP and its metabolites in order to detect an unduly high contamination due to runoff events. Conclusions  The results of the present study point out that the toxicity of 353-NP probably declines during metabolisation in water, sediment and soil, but does not vanish since the major metabolites exhibit a clear toxic potential for zebrafish embryos. Recommendations and perspectives  Metabolites of environmental pollutants should be included in the ecotoxicological test strategy for a proper risk assessment. An erratum to this article can be found at     

Biological elimination of H2S and NH3 from wastegases by biofilter packed with immobilized heterotrophic bacteria

Biotreatment of various ratios of H₂S and NH₃ gas mixtures was studied using the biofilters, packed with co-immobilized cells (Arthrobacter oxydans CH8 for NH₃ and Pseudomonas putida CH11 for H₂S). Extensive tests to determine removal characteristics, removal efficiency, removal kinetics, and pressure drops of the biofilters were performed. To estimate the largest allowable inlet concentration, a prediction model was also employed. Greater than 95% and 90% removal efficiencies were observed for NH₃ and H₂S, respectively, irrespective of the ratios of H₂S and NH₃ gas mixtures. The results showed that H₂S removal of the biofilter was significantly affected by high inlet concentrations of H₂S and NH₃. As high H₂S concentration was an inhibitory substrate for the growth of heterotrophic sulfur-oxidizing bacteria, the activity of H₂S oxidation was thus inhibited. In the case of high NH₃ concentration, the poor H₂S removal efficiency might be attributed to the acidification of the biofilter. The phenomenon was caused by acidic metabolite accumulation of NH₃. Through kinetic analysis, the presence of NH₃ did not hinder the NH₃ removal, but a high H₂S concentration would result in low removal efficiency. Conversely, H₂S of adequate concentrations would favor the removal of incoming NH₃. The results also indicated that maximum inlet concentrations (model-estimated) agreed well with the experimental values for space velocities of 50–150 h⁻¹. Hence, the results would be used as the guideline for the design and operation of biofilters.     

Acute and chronic effects of nano- and non-nano-scale TiO2 and ZnO particles on mobility and reproduction of the freshwater invertebrate Daphnia magna

Among the emerging literature addressing the biological effects of nanoparticles, very little information exists, particularly on aquatic organisms, that evaluates nanoparticles in comparison to non-nanocounterparts. Therefore, the potential effects of nano-scale and non-nano-scale TiO₂ and ZnO on the water flea, Daphnia magna, were examined in 48-h acute toxicity tests using three different test media, several pigment formulations – including coated nanoparticles – and a variety of preparation steps. In addition, a 21-d chronic Daphnia reproduction study was performed using coated TiO₂ nanoparticles. Analytical ultracentrifugation analyses provided evidence that the nanoparticles were present in a wide range of differently sized aggregates in the tested dispersions. While no pronounced effects on D. magna were observed for nano-scale and non-nano-scale TiO₂ pigments in 19 of 25 acute (48-h) toxicity tests (EC50 > 100 mg L⁻¹), six acute tests with both nano- and non-nano-scale TiO₂ pigments showed slight effects (EC10, 0.5–91.2 mg L⁻¹). For the nano-scale and non-nano-scale ZnO pigments, the acute 48-h EC50 values were close to the 1 mg L⁻¹ level, which is within the reported range of zinc toxicity to Daphnia. In general, the toxicity in the acute tests was independent of particle size (non-nano-scale or nano-scale), coating of particles, aggregation of particles, the type of medium or the applied pre-treatment of the test dispersions. The chronic Daphnia test with coated TiO₂ nanoparticles demonstrated that reproduction was a more sensitive endpoint than adult mortality. After 21 d, the NOEC for adult mortality was 30 mg L⁻¹ and the NOEC for offspring production was 3 mg L⁻¹. The 21-d EC10 and EC50 values for reproductive effects were 5 and 26.6 mg L⁻¹, respectively. This study demonstrates the utility of evaluating nanoparticle effects relative to non-nano-scale counterparts and presents the first report of chronic exposure to TiO₂ nanoparticles in D. magna.     

中小型工业窑炉NO_x废气的净化技术与应用

介绍了中小型工业窑炉生产过程中排放NOx的现状,并针对NOx的治理问题,从工程应用角度,简述了湿法和干法净化NOx的原理和化学反应过程。讨论了NOx排放特性和NOx废气中NO2/NOx比例的问题。提出了影响NOx治理的主要因素,包括吸收剂、吸附剂、催化剂和设备的部分应用参数,并结合工程实例指出工程需要注意的问题。介绍了多项采用湿法和干法净化NOx的工程应用项目,丰富了中小工业窑炉NOx废气的治理的实践经验,为中小工业窑炉排放NOx治理奠定了基础。     

Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).     

Impact of glyphosate on the development, fertility and demography of Chrysoperla externa (Neuroptera: Chrysopidae): Ecological approach

Few ecotoxicological studies have used life table analysis to evaluate the toxicity of pesticides on beneficial organisms. This study is the first report of the effect of the herbicide glyphosate on a predator insect, Chrysoperla externa, using a demographic approach. This predator is associated to soybean pests and has a potential role as a biological control agent in the Neotropical Region. The objective of this work was to evaluate the side-effects of glyphosate on the development, fertility and demography of C. externa, treated orally by ingestion of glyphosate-dipped eggs of Sitotroga cerealella in laboratory conditions. The data were analyzed using the age-stage, two-sex life table. Development from third larval instar to pupae and adult longevity were shorter in glyphosate-treatment than in the control. Adult pre-reproductive period was longer in glyphosate-treatment than in the control. Fecundity and fertility were deeply reduced, as well, being fertility greater affected. A high important reduction was registered in all population parameters. Most eggs from glyphosate-treated cohort looked abnormal, smaller than control, dehydrated and became black 2 d after oviposition. In addition, adults developed tumours in the abdomen region at 20 d after emergence, being the effect more drastic in females than males. It is beyond the scope of our study to speculate on the effects of this herbicide on C. externa field populations. However, it seems likely that populations under continuous use of glyphosate would be exposed at greater detrimental effects in the long term.     

Soil- and surfactant-enhanced reductive dechlorination of carbon tetrachloride in the presence of Shewanella putrefaciens 200

Sorption of organic contaminants to soils has been shown to limit bioavailability and biodegradation in some systems. Use of surfactants has been proposed to reverse this effect. In this study, the effects of a high organic carbon content soil and a nonionic surfactant (Triton X-100) on the reductive dechlorination of carbon tetrachloride (CCl₄) were examined in anaerobic systems containing Shewanella putrefaciens. Although more than 70% of the added CCl₄ was sorbed to the soil phase in these systems, the reductive dechlorination of CCl₄ was not diminished. Rather, rates of CCl₄ dechlorination in systems containing soil were enhanced relative to systems containing non-sorptive sand slurries. This enhancement was also observed in sterile soil slurries to which a chemical reductant, dithiothreitol was added. It appears that the organic soil used in these experiments contains some catalytic factor capable of transforming CCl₄ in the presence of an appropriate chemical or microbial reductant. The addition of Triton X-100 to sand and soil slurries containing S. putrefaciens resulted in increased CCl₄ degradation in both systems. The effect of Triton could not be explained by: (i) surfactant induced changes in the distribution of CCl₄, (i.e. decreased sorption) or the rate of CCl₄ desorption; (ii) a direct reaction between Triton and CCl₄; or (iii) increased cell numbers resulting from use of the surfactant as a substrate. Rather, it appears that Triton X-100 addition resulted in lysis of bacterial cells, a release of biochemical reductant, and enhanced reductive transformation of CCl₄. These results provide insights to guide the development of more effective direct or indirect bioremediation strategies.     

Persistence of azadirachtin A and B in soil: Effects of temperature and microbial activity

Abstract

The persistence of two insecticidally active compounds from the neem tree, azadirachtin A and B, was determined at two different temperatures (15 and 25°C) in the laboratory after application of the commercial neem insecticide, Margosan‐O, to a sandy loam soil. The influence of microbial activity on degradation was also examined by comparing autoclaved and non‐autoclaved soils also at 15 and 25°C. Temperature influenced degradation rates. The DT ₅₀ (time required for 50% disappearance of the initial concentration) for azadirachtin A was 43.9 and 19.8 d for non‐autoclaved soil kept at 15 and 25°C, respectively. The DT ₅₀ for azadirachtin B was 59.2 and 20.8 d for non‐autoclaved soil kept at 15 and 25°C, respectively. Microbial activity was also responsible for faster degradation because DT ₅₀ ’s for autoclaved soil were much longer than for non‐autoclaved soils. DT ₅₀ ‘_s for azadirachtin A in autoclaved soil were 91.2 (15°C) and 31.5 d (25°C). DT50’s for azadirachtin B in autoclaved soil were 115.5 (15°C) and 42.3 d (25°C). Two degradation products of azadirachtin were detected, but were not identified. Higher levels of the two degradation products were detected in non‐autoclaved soil.     

Effects of methanol, ethanol and n-propanol on development of Artemia salina cysts

The current study proposes an ecotoxicological test that makes use of Artemia salina cyst; the results obtained made it possible to calculate the percentage of cyst mortality (no sign of development), and growth inhibition (a delay in normal development), as well as the percentage of larva malformation, and mortality. The dehydrated cysts were directly exposed for forty-eight hours to the action of three alcohols, methanol, ethanol, and n-propanol. No teratogenic or lethal effects on larvae were found at any methanol or ethanol concentrations. Predicted values of effect concentration, EC₁, EC₁₀ and EC₅₀ were calculated from the estimated probit models for larva growth inhibition, GI, and for cyst lethal concentration, LC. At concentrations of 0.21 M methanol and 0.13 M ethanol, there were no signs of alterations in Artemia salina cyst development; these concentrations show a NOEC (No Observed Effect Concentration) value, and properly employed do not interfere with effects due to a given chemical. The n-propanol was only used to verify the extreme resistance of the dried cysts to various environmental factors.     

Euglena gracilis as a model for the study of Cu and Zn toxicity and accumulation in eukaryotic cells

We have observed the effect of copper and zinc on the biology of Euglena gracilis. The cells displayed different sensitivities to these metals, as the apparent LC₅₀ for Cu²⁺ was 0.22 mM, and for Zn²⁺ it was 0.88 mM. While Zn²⁺ was able to increase cell proliferation even at 0.1 mM, the minimal CuCl₂ concentration tested (0.02 mM) was sufficient to impair cell division. Higher concentrations of these metals not only inhibited cell division in a concentration-dependent manner, but also interfered with the metabolism of E. gracilis. A higher accumulation of proteins and lipids per cell was observed at the DI₅₀ concentration for metal-treated cells. These results suggest that the test concentration of both metals leads to a failure in completing cell division. Ultrastructural analysis indicated a chloroplast disorganization in copper-treated cells, as well as the presence of electron dense granules with different shapes and sizes inside vacuoles. Microanalysis of these granules indicated an accumulation of copper, thus suggesting a detoxification role played by the vacuoles. These results indicate that E. gracilis is an efficient biological model for the study of metal poisoning in eukaryotic cells. They also indicate that copper and zinc (copper being more poisonous) had an overall toxic effect on E. gracilis and that part of the effect can be ascribed to defects in the structure of chloroplast membranes.     

北京市交通道路空气中NO_x的污染现状及时空变化规律研究

基于2008年及2009年分4个季节对北京市3种类型道路(开阔型、交叉路口型和峡谷型)空气中的NOx的现场监测结果,分析了3种类型道路空气中NOx的污染现状和时空变化规律及影响因素。实验结果表明,昼间北京市各类型街道空气中NOx浓度呈早晚浓度高、中午浓度低的变化规律,NOx浓度随季节和车流量变化较明显。交通道路空气中NO占NOx的分担率高,且有较好的相关性,而NO2分担率较低,与NOx相关性较差。     

Regression modelling of hourly NOx and NO2 concentrations in urban air in London

Based on hourly measurements of NO_x NO₂ and O₃ and meteorological data, an ordinary least squares (OLS) model and a first-order autocorrelation (AR) model were developed to analyse the regression and prediction of NO_x and NO₂ concentrations in London. Primary emissions and wind speed are the most important factors influencing NO_x concentrations; in addition to these two, reaction of NO with O₃ is also a major factor influencing NO₂ concentrations. The AR model resulted in high correlation coefficients (R > 0.95) for the NO_x and NO₂ regression based on a whole year's data, and is capable of predicting NO₂ (R = 0.83) and NO_x (R = 0.65) concentrations when the explanatory variables were available. The analysis of the structure of regression models by Principal Component Analysis (PCA) indicates that the regression models are stable. The results of the OLS model indicate that there was an exceptional NO₂ source, other than primary emission and reaction of NO with O₃, in the air pollution episode in London in December 1991.     

Historical alteration in the nitrogen concentration and N natural abundance of mosses in Germany: Indication for regionally varying changes in atmospheric nitrogen deposition within the last 140 years

Historical alterations of nitrogen deposition in the western part of Germany were investigated by comparing nitrogen concentrations and ¹⁵N natural abundance of historical and recent samples of the two pleurocarpous mosses Pleurozium schreberi and Scleropodium purum. Pooling of the data revealed only slight tissue N increases over the past 140 years which were significant nevertheless. At closer examination on the single site level historical increases of N concentrations were found particularly for some sites in regions where agricultural activities were considerably intensified during the second half of the 20th century. The comparison of δ¹⁵N values showed a strong depletion of ¹⁵N natural abundance in areas currently heavily influenced by livestock management. This indicates an increased impact of NH_y compounds. However, the almost unchanged δ¹⁵N values in some low mountain range areas with only moderate intensification of agriculture point to a more or less constant ratio of NH_y/NO_x input over time. Significant correlations of both tissue N concentrations and ¹⁵N natural abundance between the two species justify the assumption that they use the same nitrogen source, probably atmospheric deposition.     

Distribution coefficients (Kd) and desorption rates of Cs and Am in Black Sea sediments

The distribution coefficients (K_d) and desorption rates of ¹³⁷Cs and ²⁴¹Am radionuclides in bottom sediments at different locations in the Black Sea were studied under laboratory conditions. The K_d values were found to be 500 for ¹³⁷Cs and 3800 for ²⁴¹Am at the steady state and described exponential curves. Rapid uptake of the radionuclides occurred during the initial period and little accumulation happened after four days. The desorption rates for ¹³⁷Cs in different bottom sediments were best described by a three-component exponential model. The desorption half-times of ¹³⁷Cs ranged from 26 to 50 d at the slow components. However, the desorption rate of ²⁴¹Am described one component for all sediment samples and desorption half-time was found to be 75 d. In general, the results showed that the ²⁴¹Am radionuclide is more effectively transferred to bottom sediment and has longer turnover time than ¹³⁷Cs under Black Sea conditions.     

Trophic transfer of pyrene metabolites and nonextractable fraction from Oligochaete (Lumbriculus variegatus) to juvenile brown trout (Salmo trutta)

Cell lines of Etroplus suratensis established in our laboratory were evaluated for their potential use as screening tools for the ecotoxicological assessment of tannery effluent. The cytotoxic effect of tannery effluent in three cell lines derived from eye, kidney and gill tissue of E. suratensis was assessed using multiple endpoints such as Neutral Red (NR) assay, Coomassie Blue (CB) protein assay and Alamar Blue (AB) assay. Acute toxicity tests on fish were conducted by exposing E. suratensis for 96 h to tannery effluent under static conditions. The toxic effect of tannery effluent on the survival of fish was found to be concentration and time dependent. The tannery effluent at the concentration of 15% caused 100% mortality at 96 h whereas the lower concentration (0.5%) caused 13.33% mortality. The cytotoxicity of tannery effluent was found to be similar in the three cell lines tested, independent of the toxic endpoints employed. EC₅₀ values, the effective concentration of tannery effluent resulting in 50% inhibition of cytotoxicity parameters after 48 h exposure to tannery effluent were calculated for eye, kidney and gill cell lines using NR uptake, AB and cell protein assays. Statistical analysis revealed good correlation with r² = 0.95-0.99 for all combinations between endpoints employed. Linear correlations between each in vitro EC₅₀ and the in vivo LC₅₀ data, were highly significant p < 0.001 with r² = 0.977, 0.968 and 0.906 for AB₅₀, NR₅₀, and CB₅₀, respectively.