Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Age-specific life tagle of red cotton stainer (fabricius) (hemiptera: Pyrrhocoridae)

The present studies on the age-specific life table of red cotton stainer suggest that the eggs and the initial immature stages are the most suceptible ones and a control measure if inflicted upon these, it might fetch the maximum result with the minimum usage of hazardous poisonous chemicals.     

As(V) and Sb(V) co-adsorption onto ferrihydrite: synergistic effect of Sb(V) on As(V) under competitive conditions

Competitive adsorption of As(V) and Sb(V) at environmentally relevant concentrations onto ferrihydrite was investigated. Batch experiments and XPS analyses confirmed that in a binary system, the presence of Sb(V) exhibited a slight synergistic effect on As(V) adsorption. XPS analyses showed that As(V) and Sb(V) adsorption led to obvious diminishment of Fe–O–Fe and Fe–O–H bonds respectively. At pH of 9, a more significant decrease of Fe–O–Fe was observed in the binary system than that in a single system, indicating that As(V) displayed an even stronger interaction with lattice oxygen atoms under competitive conditions. Basically, ionic strength demonstrated a negligible or positive influence on As(V) and Sb(V) adsorption in binary system. Study of adsorption sequence also indicated that the presence of Sb(V) showed a promotion effect on As(V) adsorption at neutral pHs. Considering that co-contamination of As and Sb in waters has been of great concern throughout the world, our findings contributed to a better understanding of their distribution, mobility, and fate in environment.

     

Estimating K(oc) for persistent organic pollutants: limitations of correlations with K(ow)

The n-octanol/water partition coefficient (K(ow)) is commonly used to predict the soil or aquatic particle water partition coefficient normalized to organic carbon (K(oc)). Many correlations are available covering several chemical classes and ranges of hydrophobicity. This work indicates the K(ow) may not be a strong predictor for persistent organic pollutants (POPs) which are defined here as chemicals with logK(ow) > 5.0. In addition, the correlation developed in this work for POPs will still result in a predicted value which is of by a factor of 15. Accordingly, care must be taken when applying K(oc) estimations using K(ow) for POPs until more suitable correlations are developed.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Effects of five insecticides used in apple orchards on Hyaliodes vitripennis (Say) (Hemiptera: Miridae)

Azinphos-methyl, carbaryl, dimethoate, phosmet and phosalone were used in apple orchards to manage apple aphid, apple maggot, woolly apple aphid and leaf eating caterpillars. Among the five insecticides evaluated, dimethoate, carbaryl and azinphosmethyl were the most toxic to the nymphs and adults of Hyaliodes vitripennis (Say) from two regions. Phosalone was the least toxic. Nymphs were more resistant than the adults. While the LC50 for dimethoate was 130 ppm for nymphs, it was 3 ppm for adults from St. Jean-Baptiste-de-Rouville. There were also significant differences in the level of resistance between the two regions where the H. vitripennis were collected. At St. Alexandre the LC50 for phosalone on nymphs was 19,250 ppm whereas, at St. Jean-Baptiste-de-Rouville it was 160,000 ppm.     

(M)VOC and composting facilities. Part 2: (M)VOC dispersal in the environment

BACKGROUND, AIMS AND SCOPE: Composting facilities are known to release odorous volatiles due to biodegradation of municipal waste and plant residues. Although odour perception and its grading is influenced by experience, attitude and adaptation, these emissions have created a lack of acceptance for residents in the vicinity of composting facilities. Enclosure of compost pile halls, ventilation systems and biofilters are often insufficient to minimise the burden of compost-derived compounds in the air. Moreover, economic considerations forced smaller communities to establish less sophisticated facilities with open storage areas and other relevant sources for wind-borne dispersal of bioaerosols. Aim of the present study was to characterise the immission and dispersal of microbial volatiles (MVOC) and, besides, to find coincidences between MVOC and compost odour. METHODS: In the course of this study, the surroundings of two composting facilities, differing in their type of process engineering, were investigated for emission of volatiles in the environment. Both microbially and plant-derived substances were assessed, several of which have low odour thresholds. Air samples were taken in distances ranging from 50 to 800 m in a downwind direction from each facility. RESULTS AND DISCUSSION: Compost-derived and microbial volatile organic compounds (MVOC) were found at distances of up to 800 m from the composting facilities. Terpenes like alpha-pinene, camphene and camphor were the dominant compounds and coincided with typical compost odour, whereas several typical MVOC were not found at greater distances. The terpenes in combination with certain MVOC may play an important role in the perception of compost odour. Exposure concentrations were not of toxicological relevance, but sensory irritation and psychohygienic effects due to an annoyance potential of such compounds should not be dismissed. RECOMMENDATIONS AND OUTLOOK: Although terpenes are generally associated with pleasant odour characteristics, they seemed to contribute to malodours in a mixture with other VOC, in this context of volatile waste from compost facilities. Malodorous emissions from biowaste have to be considered as sources of health complaints and the investigation of mixtures of compost-derived volatiles is still inevitable. Exposure levels have to be discussed taking VOC mixtures into account. Within composting facilities, technical devices have to be improved to minimise dispersal of volatiles to prevent residents from immissions eventually causing health complaints.     

PAH Metabolites in Bile Fluids of Dab (Limanda limanda) and Flounder (Platichthys flesus): Spatial Distribution and Seasonal Changes (7 pp)

Background, Aim and Scope Polycyclic aromatic hydrocarbons (PAH) are important environmental contaminants which may lead to increased levels of neoplastic aberrations or tumours in fish liver. Therefore, monitoring of PAH and their effects are part of several international environmental programmes. The aim of the present field study was to investigate the concentrations of the PAH metabolites in fish bile, to elucidate spatial, seasonal and species differences as well as to discuss different strategies of normalisation with regard to environmental monitoring. Materials and Methods: PAH metabolites were determined in the bile fluid of dab (Limanda limanda) and flounder (Platichthys flesus) caught in the North Sea and Baltic Sea between 1997 and 2004. After enzymatic deconjugation, two metabolites were determined by means of HPLC. The limit of detection and the limit of quantification were calculated. The accuracy of the method was tested with a standard reference material. Results were referred to bile volume as well as to biliverdin. Results: The main metabolite, 1-hydroxypyrene, was determined in concentrations from <0.7 to 838 ng/ml in bile of dab (Limanda limanda) and flounder (Platichthys flesus) caught between 1997 and 2004. The values for 1-hydroxyphenanthrene in fish bile were considerably lower (<0.4 – 87 ng/ml). Significant differences in the 1-hydroxypyrene levels were found between summer and winter surveys as well as between the sampling sites in the data set from 2004 (383 dabs and 62 flounders): Highest levels of PAH contamination were found in dab from the German Bight and in flounder from the Baltic Sea. Discussion: Spatial differences in 1-hydroxypyrene concentrations between North Sea and Baltic Sea were discussed, as well as differences in relation to season, sex and species. Three parameters of normalisation (biliary protein, biliverdin and bile pigments) were discussed. Biliverdin was identified as a suitable parameter for the normalisation of PAH metabolites in field samples. Conclusions: Spatial differences in 1-hydroxypyrene concentrations of dab demonstrate the usefulness of PAH metabolites in fish bile as a monitoring parameter in marine regions. Significant differences in 1-hydroxypyrene concentrations were found between summer and winter sampling campaigns. This may be linked to an annual cycle of 1-hydroxyprene in dab. It is also possible that bile synthesis/release in dab differs between the seasons. There is no indication for a time trend from 1997 to 2004. Recommendations and Perspectives: It is recommended to relate PAH metabolites in fish bile to biliverdin concentrations. Although the concentrations are low in offshore regions and bile volumes are small, the method presented here allows one to measure PAH metabolites on an individual level which is a crucial prerequisite for meaningful monitoring studies.     

Formation of Disinfection Byproducts (DBPs) in Surface Water Sources: Differential Ultraviolet (UV) Absorbance Approach

Chlorination for drinking water forms various disinfection byproducts (DBPs) of trihalomethanes (THMs) and haloacetic acids (HAAs). Chlorination has been attributed to the destruction of activated aromatic sites of the natural organic matter (NOM) predominantly at electron rich sites. Experiments with Istanbul surface waters showed that the magnitude of the decrease in the ultraviolet (UV) absorbance at 272 nm (UV₂₇₂) was an excellent indicator of destruction of these sites by chlorine. The main objective of the present study is to develop the differential UV₂₇₂ absorbance (ΔUV₂₇₂) related models for the prediction of the formation of THM, HAA, and their species in raw water samples from Terkos, Buyukcekmece, and Omerli lakes under different chlorination conditions. Significant factors affecting DBP formation in the raw waters were identified through numerical and graphical techniques. The R² values of the models varied between 0.94 and 0.97, indicating excellent predictive ability for THM₄ and HAA₉ in the raw waters. The models were validated using additional data. The results of this study concluded that addition of ΔUV₂₇₂ parameter into THM₄ and HAA₉ models make the prediction of these DBP compounds more precisely than those of DBP models developed in the past. A better understanding of these modeling systems will help the water treatment plant operators to minimize the DBP formation, providing a healthier and better drinking water quality as well as identifying strategies to improve water treatment and disinfection processes.     

Effects of five insecticides used in apple orchards on Hyaliodes vitripennis (say) (Hemiptera: Miridae)

Abstract

Azinphos‐methyl, carbaryl, dimethoate, phosmet and phosalone were used in apple orchards to manage apple aphid, apple maggot, woolly apple aphid and leaf eating caterpillars. Among the five insecticides evaluated, dimethoate, carbaryl and azinphosmethyl were the most toxic to the nymphs and adults of Hyaliodes vitripennis (Say) from two regions. Phosalone was the least toxic. Nymphs were more resistant than the adults. While the LC₅₀ for dimethoate was 130 ppm for nymphs, it was 3 ppm for adults from St. Jean‐Baptiste‐de‐Rouville. There were also significant differences in the level of resistance between the two regions where the H. vitripennis were collected. At St. Alexandre the LC₅₀ for phosalone on nymphs was 19, 250 ppm whereas, at St. Jean‐Baptiste‐de‐Rouville it was 160, 000 ppm.     

Herbicide toxicity,selectivity and hormesis of nicosulfuron on 10 Trichogrammatidae (Hymenoptera) species parasitizing Anagasta ( = Ephestia) kuehniella (Lepidoptera: Pyralidae) eggs

Selective agrochemicals including herbicides that do not affect non-target organisms such as natural enemies are important in the integrated pest management (IPM) programs. The aim of this study was to evaluate the herbicide toxicity, selectivity and hormesis of nicosulfuron, recommended for the corn Zea mays L. (Poaceae) crop, on 10 Trichogrammatidae (Hymenoptera) species. A female of each Trichogramma spp. or Trichogrammatoidea annulata De Santis, 1972 was individually placed in plastic test tubes (no choice) with a cardboard containing 45 flour moth Anagasta ( = Ephestia) kuehniella Zeller, 1879 (Lepidoptera: Pyralidae) eggs. Parasitism by these natural enemies was allowed for 48 h and the cardboards were sprayed with the herbicide nicosulfuron at 1.50 L.ha^?1, along with the control (only distilled water). Nicosulfuron reduced the emergence rate of Trichogramma bruni Nagaraja, 1983 females, but increased that of Trichogramma pretiosum Riley, 1879, Trichogramma acacioi Brun, Moraes and Smith, 1984 and T. annulata females. Conversely, this herbicide increased the emergence rate of Trichogramma brasiliensis Ashmead, 1904, T. bruni, Trichogramma galloi Zucchi, 1988 and Trichogramma soaresi Nagaraja, 1983 males and decreased those of T. acacioi, Trichogramma atopovilia Oatman and Platner, 1983 and T. pretiosum males. In addition, nicosulfuron reduced the sex ratio of T. galloi, Trichogramma bennetti Nagaraja and Nagarkatti, 1973 and T. pretiosum and increased that of T. acacioi, T. bruni, T. annulata, Trichogramma demoraesi Nagaraja, 1983, T. soaresi and T. brasiliensis. The herbicide nicosulfuron was “harmless” (class 1, <30% reduction) for females and the sex ratio of all Trichogrammatidae species based on the International Organization for Biological Control (IOBC) classification. The possible hormesis effect of nicosulfuron on Trichogrammatidae species and on the bacterium Wolbachia sp. (Rickettsiales: Rickettsiaceae) was also discussed.     

Dioxins: WHO's tolerable daily intake (TDI) revisited

In December 1990, the World Health Organization (WHO) established a tolerable daily intake (TDI) of 10 pg/kg b.w. (body weight) for TCDD, based on liver toxicity, reproductive effects and immunotoxicity in experimental animals, and making use of kinetic data in humans and experimental animals. Since then new epidemiological and toxicological data have emerged, in particular with respect to neurodevelopmental and endocrine effects of dioxin. Therefore, the European Centre for Environment and Health of the World Health Organization (WHO-ECEH) and the International Programme on Chemical Safety (IPCS) jointly organized a consultation on the "Assessment of the health risk of dioxins: re-evaluation of the TDI", May 1998, Geneva, Switzerland. The participants discussed the health risks for infants, cancer and non-cancer endpoints in humans and animals, mechanistic aspects, kinetic behaviour, modelling, exposure, and the applicability of the toxic equivalency (TEQ) concept. For the health risk assessment of dioxin-like compounds, the WHO Consultation focused on the most sensitive effects that are considered adverse (hormonal, reproductive and developmental effects) seen at low doses in animal studies (rats and monkeys). Human daily intakes corresponding with body burdens similar to those associated with adverse effects in animals could be estimated to be in the range of 14-37 pg/kg b.w./day. To arrive at a TDI expressed as TEQ, a composite uncertainty factor of 10 was recommended. By applying this uncertainty factor a TDI range of 1-4 pg TEQs/kg body weight was established. An extensive executive summary of the results of this WHO Consultation with all the underlying background documents will be published in Food Additives and Contaminants (in press).     

Complications with using ratios for environmental data: comparing enantiomeric ratios (ERs) and enantiomer fractions (EFs)

Complications arise when ratios are used to present environmental data because ratios are an unbounded, multiplicative scale that can lead to asymmetrical (skewed) data distributions. Enantiomeric ratios (ERs), historically used in discussions of chiral signatures, often are published as mean ER+/-single-value standard deviation. Application of statistical summaries, such as the widely used sample mean and standard deviation, to skewed ratio data is misleading and often inappropriate. Comparison of statistically summarized ER and enantiomer fraction (EF) data (which are based on a bounded, additive scale) for a range of hypothetical values reveals substantial discrepancies when conversion between ER and EF formats is used. These discrepancies are largest when the ratio data are greater than one and have large variability, because the data are more skewed. In many cases, the use of fractions instead of ratios can help to minimize misrepresentation of environmental data, including chiral data. The use of nonparametric statistical summaries, e.g., median and percentiles, provides a more robust indicator of the typical value and spread for both ER and EF data.     

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) isomer patterns from municipal waste combustion: formation mechanism fingerprints

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.     

Population growth of Euchlanis dilatata (Rotifera): combined effects of methyl parathion and food (Chlorella vulgaris)

In the present work, the combined impact of four concentrations (0, 0.0625, 0.125, and 0.25 mg/L) of methyl parathion and three densities (0.5 x 10(6), 1.0 x 10(6), and 2.0 x 10(6) cells/mL) of the green alga Chlorella vulgaris on the population growth of Euchlanis dilatata was studied. In general, regardless of the food level, an increase in the concentration of methyl parathion resulted in a significant reduction of the maximal population density and rate of population increase. The population growth rate in the controls ranged from 0.248 to 0.298; rates were lower in the presence of the pesticide. At any toxicant concentration, rotifers fed higher algal density showed significantly higher population growth compared with those at lower food levels. An interaction between toxicant and food level was evident on the population growth of E. dilatata. Results have been discussed in light of the protective role of algal density on the toxic effects of insecticides on rotifers and the differences in susceptibility to toxicants between planktonic and littoral rotifers.