A Strategy for the Evaluation of Sensory and Pulmonary Irritation Due to Chemical Emissions from Indoor Sources

Abstract

Sensory and pulmonary irritation are physiological responses to chemical exposure which result in characteristic, measurable changes in respiratory activity in mice. A standard method has been applied to the estimation of sensory irritation associated with a specific chemical exposure. This method has been correlated with human responses to these chemicals. Symptoms associated with chemical irritants are consistent with complaints due to problems with indoor air quality, which may include eye and upper respiratory tract irritation, headaches, and nausea. A stepwise strategy for assessing the contribution of indoor products to sensory and pulmonary irritation is discussed in the current paper. The strategy includes product emissions testing using dynamic environmental chambers, the selection of suspected irritants for respiratory irritation testing, respiratory irritation testing of individual compounds and representative mixtures using synthesized atmospheres, and the evaluation of test data to determine those compounds which may contribute to sensory and pulmonary irritation in humans. The current strategy is being applied to evaluate carpet system materials and their constituent chemicals.     

Evaluation of age, gender and regional concentration differences for dioxin-like chemicals in the Australian population

The results of this study provide a measure of the levels of dioxin-like compounds (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls) in pooled blood serum collected throughout Australia in 2003. De-identified samples selected from surplus pathology samples were stratified on the basis of gender, region and age. In total 9090 samples were collected and analysed as 96 pools. Dioxin-like chemicals were detected in all strata. The mean and median levels expressed as TEQ values for all pooled samples were 10.9+/-1.0 pg TEQ g(-1) lipid and 8.3 pg TEQ g(-1) lipid. For males and females the mean levels were 10.4+/-0.6 pg TEQ g(-1) lipid and 11.5+/-1.5 pg TEQ g(-1) lipid, respectively. A direct relationship of increasing dioxin-like chemical levels with increasing age was observed and could be described by the following equation: Levels in blood expressed as pg TEQ g(-1) lipid = 3.3 exp(0.0251 age) (r2 = 0.87). No significant differences were observed in the levels of dioxin-like chemicals in samples collected from males and females. In addition, the levels of dioxin-like chemicals across the five regions were similar within each age range. In summary, the levels of dioxin-like chemicals in the Australian population are low compared to international levels and are similar across all regions of Australia within each designated age range. The levels of these chemicals increase with age and can be estimated if the age of an individual is known.     

The OECD Validation Program of the H295R Steroidogenesis Assay for the Identification of In Vitro Inhibitors and Inducers of Testosterone and Estradiol Production. Phase 2: Inter-Laboratory Pre-Validation Studies (8 pp)

Background, Goals and Scope In response to concerns that have been raised about chemical substances that may alter the function of endocrine systems and result in adverse effects on human health, an OECD initiative was undertaken to develop and validate in vitro and in vivo assays to identify chemicals that may interfere with endocrine systems of vertebrates. Here we report on studies that were conducted to develop and standardize a cell-based screening assay using the H295R cell line to prioritize chemicals that may act on steroidogenic processes in humans and wildlife. These studies are currently ongoing as part of the ‘Special Activity on the Testing and Assessment of Endocrine Disruptors’ within the OECD Test Guidelines Program to review, develop, standardize, and validate a number of in vitro and in vivo toxicological assays for testing and assessment of chemicals concerning their potential to interact with the endocrine system of vertebrates. Study Design Six laboratories from five countries participated in the pre-validation studies. Each laboratory tested the effects of three model chemicals on the production of testosterone (T) and estradiol (E2) using the H295R Steroidogenesis Assay. Chemicals tested were well described inducers or inhibitors of steroidogenic pathways (forskolin, prochloraz and fadrozole). All experiments were conducted in 24 well plates following standard protocols. Six different doses per compound were analyzed in triplicate per plate. A quality control (QC) plate was run in conjunction with the chemical exposure plate to account for inter-assay variation. Each chemical exposure was conducted two or three times. Results All laboratories successfully detected increases and/or decreases in hormone production by H295R cells after exposure to the different model compounds and there was good agreement in the pattern of response for all groups. Forskolin increased both T and E2 while fadrozole and prochloraz decreased production of both hormones. All chemicals affected hormone production in a dose-dependent manner with the exception of fadrozole which caused maximum inhibition of E2 at the two least concentrations tested. Some inter-laboratory differences were noted in the alteration of hormone production measured in chemically exposed cells. However, with the exception of the production of T measured at one laboratory in cells exposed to forskolin, the EC₅₀s calculated were comparable (coefficients of variation 34–49%) for all hormones. Discussion and Perspectives The results indicated that the H295R Steroidogenesis Assay protocol was robust, transferable and reproducible among all laboratories. However, in several instances that were primarily related to one laboratory there were unexplained minor uncertainties related to the inter-laboratory hormone production variation. Based on the findings from this Phase 2 prevalidation study, the H295R Steroidogenesis Assay protocol is currently being refined. The next phase of the OECD validation program will test the refined protocol among the same group of laboratories using an extended set of chemicals (∼30) that will include positive and negative chemical controls as well as a broad spectrum of different potential inducers and inhibitors of steroidogenic pathways. Submission Editor: Dr. Carsten Brühl (bruehl@uni-landau.de)     

Depressed prostaglandins and leukotrienes in veterans with Gulf War illness

Background: There is need to understand biological markers and mechanisms in Gulf War illness (GWI).

Goal: To examine whether and how eicosanoids – prostaglandins and leukotrienes – are altered in veterans with GWI.

Methods: Seventy participants including 37 GWI and 33 healthy controls, shared exposure information, and had plasma eicosanoids assessed – prostaglandin F2 alpha (pgf2α), prostaglandin D2 (pgd2), leukotriene B4 (lb4) among others. Values were compared for GWI versus controls. Eicosanoid intercorrelations were compared in cases vs. controls. For the most significantly altered eicosanoid in GWI, exposure and symptom relations were assessed.

Results: Prostaglandins and leukotrienes were depressed in GWI, strongest for pgf2α, then lb4. Eicosanoid intercorrelations differed in GWI vs. controls. Fuel-solvent, pesticide, radioactive chemicals and metal exposures related negatively to pgf2α; as, in GWI, did chemical attack and vaccines. Multivariate predictors included fuels-solvents and radioactive chemicals (negative); tetanus vaccine and herbicides (positive). Fuels-solvents and radioactive chemicals predicted lower pgf2α in cases, controls, and all participants controlled for case status. Lower pgf2α related to GWI “Kansas criteria” domains of pain, respiratory, and (borderline significantly) skin symptoms.

Conclusion: Multiple eicosanoids are depressed in GWI, particularly pgf2α and lb4. Prior fuel-solvent exposures, radioactive chemicals, and (in GWI cases) vaccines were linked to lower pgf2α.     

The effects of ammonium sulphate and urea upon egg hatching and miracidial survival of Schistosoma mansoni

Abstract

The effects of various concentrations of ammonium sulphate and urea on egg hatching and miracidial survival of S. mansoni were tested in order to determine if the use of these fertilizers in the ricelands of the Republic of Cameroon could affect the transmission of schistosomiasis. Results indicate that hatching of eggs and survival of miracidia varied with concentrations of tested chemicals and times of exposure. Exposure of S. mansoni eggs to 0.20%‐1.00% ammonium sulphate or to 0.50%‐4.00% urea reduced their ability to hatch and produce miracidia. A chemical concentration of 1.00% ammonium sulphate or 4.00% urea was found to be sufficient to produce complete inhibition of hatching. High concentrations of both chemicals not only inhibited miracidial emmergence but also may be ovocidal. Results obtained from miracidial survival tests indicated that LC₅, LC₅₀ and LC₉₅ values for ammonium sulphate were 0.07%, 0.80% and 10.61% after 2 hours of exposure; 0.03%, 0.16% and 0.90% after 4 hours of exposure; and 0.30%, 0.20% and 0.40% after 6 hours of exposure respectively. Similar statistical analyses revealed that the LC₅, LC₅₀ and LC₉₅ values for urea were 0.22%, 1.90% and 16.25% after 2 hours of exposure; 0.28%, 0.57% and 1.14% after 4 hours of exposure; and 0.13%, 0.27% and 0.57%” after 6 hours of exposure respectively. Although the two fertilizers exerted some adverse effects on S. mansoni eggs and miracidia at relatively high concentrations, neither of them was found to be of practical value. Ammonium sulphate and urea concentrations effective in killing S. mansoni eggs and miracidia were about one to two orders of magnitude greater than the actual field application rates.     

A fluorescence-based bioassay for aquatic macrophytes and its suitability for effect analysis of non-photosystem II inhibitors

Background, Goals and Scope During the last years the miniaturization of toxicity test systems for rapid and parallel measurements of large quantities of samples has often been discussed. For unicellular algae as well as for aquatic macrophytes, fluorescence-based miniaturized test systems have been introduced to analyze photosystem II (PSII) inhibitors. Nevertheless, high-throughput screening should also guarantee the effect detection of a broad range of toxicants in order to ensure routinely applicable, high-throughput measuring device experiments which can cover a broad range of toxicants and modes of action others than PSII inhibition. Thus, the aim of this study was to establish a fast and reproducible measuring system for non-PSII inhibitors for aquatic macrophyte species to overcome major limitations for use. Methods A newly developed imaging pulse-amplitude-modulated chlorophyll fluorometer (I-PAM) was applied as an effect detector in short-term bioassays with the aquatic macrophyte species Lemna minor. This multiwell-plate based measuring device enabled the incubation and measurement of up to 24 samples in parallel. The chemicals paraquat-dichloride, alizarine and triclosan were chosen as representatives for the toxicant groups of non-PSII herbicides, polycyclic aromatic hydrocarbons (PAHs) and pharmaceuticals and personal care products (PPCPs), which are often detected in the aquatic environment. The I-PAM was used (i) to establish and validate the sensitivity of the test system to the three non-PSII inhibitors, (ii) to compare the test systems with standardized and established biotests for aquatic macrophytes, and (iii) to define necessary time scales in aquatic macrophyte testing. For validation of the fluorescence-based assay, the standard growth test with L. minor (ISO/DIS 20079) was performed in parallel for each chemical. Results The results revealed that fluorescence-based measurements with the I-PAM allow rapid and parallel analysis of large amounts of aquatic macrophyte samples. The I-PAM enabled the recording of concentration-effect-curves with L. minor samples on a 24-well plate with single measurements. Fluorescence-based concentration-effect-curves could be detected for all three chemicals after only 1 h of incubation. After 4–5 h incubation time, the maximum inhibition of fluorescence showed an 80–100% effect for the chemicals tested. The EC50 after 24 h incubation were estimated to be 0.06 mg/L, 0.84 mg/L and 1.69 mg/L for paraquatdichloride, alizarine and triclosan, respectively. Discussion The results obtained with the I-PAM after 24 h for the herbicide paraquat-dichloride and the polycyclic aromatic hydrocarbon alizarine were in good accordance with median effective concentrations (EC50s) obtained by the standardized growth test for L. minor after 7 d incubation (0.09 mg/L and 0.79 mg/L for paraquat-dichloride and alizarine, respectively). Those results were in accordance with literature findings for the two chemicals. In contrast, fluorescence-based EC50 of the antimicrobial agent triclosan proved to be two orders of magnitude greater when compared to the standard growth test with 7 d incubation time (0.026 mg/L) as well as with literature findings. Conclusion Typically, aquatic macrophyte testing is very time consuming and relies on laborious experimental set-ups. The I-PAM measuring device enabled fast effect screening for the three chemicals tested. While established test systems for aquatic macrophytes need incubation times of ≥ 7 d, the I-PAM can detect inhibitory effects much earlier (24 h), even if inhibition of chemicals is not specifically associated with PSII. Thus, the fluorescence-based bioassay with the I-PAM offers a promising approach for the miniaturization and high-throughput testing of chemicals with aquatic macrophytes. For the chemical triclosan, however, the short-term effect prediction with the I-PAM has been shown to be less sensitive than with long-term bioassays, which might be due to physicochemical substance properties such as lipophilicity. Recommendations and Perspectives The results of this study show that the I-PAM represents a promising tool for decreasing the incubation times of aquatic macrophyte toxicity testing to about 24 h as a supplement to existing test batteries. The applicability of this I-PAM bioassay on emergent and submerged aquatic macrophyte species should be investigated in further studies. Regarding considerations that physicochemical properties of the tested substances might play an important role in microplate bioassays, the I-PAM bioassay should either be accompanied by evaluating physicochemical properties modeled from structural information prior to an experimental investigation, or by intensified chemical analyses to identify and determine nominal concentrations of the toxicants tested. The chemicals paraquat-dichloride, alizarine and triclosan were chosen as representatives for the toxicant groups of non-PSII herbicides, PAHs and PPCPs which are often detected in the aquatic environment. Nevertheless, in order to ensure a routinely applicable measuring device, experiments with a broader range of toxicants and samples of surface and/or waste waters are necessary. ESS-Submission Editor: Dr. Markus Hecker (MHecker@Entrix.com)     

Effect of Periods of Non-Use on Biofilter Performance

Abstract

A biofilter does not operate as a true filter, but removes chemicals from gases by sorption and biologically degrades them. The objective of the research reported in this paper was to investigate the effect of periods of non-use on biofilter performance. The concept of non-use had two meanings in this research: "no chemical loading," which indicated that humidified air was passing through the biofilter with no chemicals, and "stagnant," which reflected that no flow at all was passing through the biofilter. Both instances of nonuse can require the microorganisms in the biofilter to reacclimate to differences in loading and type of chemical when a chemical load is re-applied. Acclimation time was compared with three different chemicals, initial acclimation was compared with re-acclimation following different periods of non-use, and the effect of humidification during the period of non-use was examined.

Bench scale testing produced results indicating that acclimation times ranged from several hours to longer than a day. Longer periods of biofilter non-use resulted in longer reacclimation periods and transition between different chemicals resulted in acclimation periods shorter than initial acclimation periods. Stagnant periods produced longer re-acclimation periods than periods of no chemical loading.     

The OECD validation program of the H295R steroidogenesis assay: Phase 3. Final inter-laboratory validation study

Background, goals, and scope

In response to increasing concerns regarding the potential of chemicals to interact with the endocrine system of humans and wildlife, various national and international programs have been initiated with the aim to develop new guidelines for the screening and testing of these chemicals in vertebrates. Here, we report on the validation of an in vitro assay, the H295R steroidogenesis assay, to detect chemicals with the potential to inhibit or induce the production of the sex steroid hormones testosterone (T) and 17??-estradiol (E2) in preparation for the development of an Organization for Economic Cooperation and Development (OECD) test guideline.

Methods

A previously optimized and pre-validated protocol was used to assess the potential of 28 chemicals of diverse structures and properties to validate the H295R steroidogenesis assay. These chemicals are comprised of known endocrine-active chemicals and ??negative?? chemicals that were not expected to have effects on the targeted endpoints, as well as a number of test chemicals with unknown modes of action at the level of the steroidogenic pathway. A total of seven laboratories from seven countries participated in this effort. In addition to effects on hormone production, confounding factors, such as cell viability and possible direct interference of test substances with antibody-based hormone detection assays, were assessed. Prior to and during the conduct of exposure experiments, each laboratory had to demonstrate that they were able to conduct the assay within the margin of predefined performance criteria.

Results

With a few exceptions, all laboratories met the key quality performance parameters, and only 2% and 7% of all experiments for T and E2, respectively, were excluded due to exceedance of these parameters. Of the 28 chemicals analyzed, 13 and 14 tested affected production of T and E2, respectively, while 11 and 8 did not result in significant effects on T and E2 production, respectively. Four and six chemicals produced ambiguous results for effects on T and E2 production, respectively. However, four of these cases each for T and E2 were associated with only one laboratory after a personnel change occurred. Significant interference of test chemicals with some of the antibody-based hormone detection systems occurred for four chemicals. Only one of these chemicals, however, significantly affected the ability of the detection system to categorize the chemical as affecting E2 or T production.

Discussion and conclusions

With one exception, the H295R steroidogenesis assay protocol successfully identified the majority of chemicals with known and unknown modes of interaction as inducers or inhibitors of T and E2 production. Thus it can be considered a reliable screen for chemicals that can alter the production of sex steroid hormones. One of the remaining limitations associated with the H295R steroidogenesis assay protocol is the relatively small basal production of E2 and its effect on quantifying the decreased production of this hormone with regard to the identification of weak inhibitors. An initial comparison of the data produced in this study with those from in vivo studies from the literature demonstrated the potential of the H295R steroidogenesis assay to identify chemicals affecting hormone homeostasis in whole organisms. Particularly promising was the lack of any false negatives during the validation and the very low number of false positives (1 out of 28 chemicals for each T and E2).

Perspectives

Based on the results obtained during this validation study and the accordingly revised test protocols, an OECD draft test guideline was developed and submitted to the OECD working group of the national coordinators of the test guidelines program (WNT) for comments in December 2009.     

First report on development of quantitative interspecies structure-carcinogenicity relationship models and exploring discriminatory features for rodent carcinogenicity of diverse organic chemicals using OECD guidelines

Different regulatory agencies in food and drug administration and environmental protection worldwide are employing quantitative structure-activity relationship (QSAR) models to fill the data gaps related with properties of chemicals affecting the environment and human health. Carcinogenicity is a toxicity endpoint of major concern in recent times. Interspecies toxicity correlations may provide a tool for estimating sensitivity towards toxic chemical exposure with known levels of uncertainty for a diversity of wildlife species. In this background, we have developed quantitative interspecies structure-carcinogenicity correlation models for rat and mouse [rodent species according to the Organization for Economic Cooperation and Development (OECD) guidelines] based on the carcinogenic potential of 166 organic chemicals with wide diversity of molecular structures, spanning a large number of chemical classes and biological mechanisms. All the developed models have been assessed according to the OECD principles for the validation of QSAR models. Consensus predictions for carcinogenicity of the individual compounds are presented here for any one species when the data for the other species are available. Informative illustrations of the contributing structural fragments of chemicals which are responsible for specific carcinogenicity endpoints are identified by the developed models. The models have also been used to predict mouse carcinogenicities of 247 organic chemicals (for which rat carcinogenicities are present) and rat carcinogenicities of 150 chemicals (for which mouse carcinogenicities are present). Discriminatory features for rat and mouse carcinogenicity values have also been explored.     

Fragrances in the Environment: Pleasant odours for nature? (9 pp)

Goal, Scope and Background Fragrance preparations or perfumes are used in an increasing variety of applications, as for example washing, cleansing, personal care products, consumer goods or in applications to modify indoor air. However, up to now, little is known to the general or scientific public about their chemical identity and the use pattern of single substances, not even for high production volume chemicals. Some toxicological data are published for a comparatively small number of substances with a focus on sensitisation and dermal effects, while other effects are neglected. Information on ecotoxicity and environmental fate are rare, especially for long-term exposure. Data for a detailed hazard and risk analysis are available in exceptional cases only. According to the current legal situation, fragrance industry is self-regulated, which means that pre-market risk evaluation is not required for most fragrances. Odour and the ability to smell play a major role for wildlife for all taxonomic groups. Reproductive and social behaviour, defence, communication and orientation depend on volatile compounds which can be identical to those used in fragrance preparations. Our interdisciplinary approach leads to the question of whether and, if so, to what extent anthropogenic fragrances may influence life and reproduction of organisms in the environment. Main Features Information from literature on use, exposure and biological effects was combined to analyse the state of knowledge. Following an overview of the amounts of fragrances used in different consumer products and their release into the environment, the roles of odours in nature are shown for a selection of compounds. Existing regulation was analysed to describe the data basis for environmental risk evaluation. Finally, recommendations for further action are derived from these findings. Results Three main results were elaborated: First, fragrance substances are continuously discharged in large amounts into the environment, especially via the waste water. Second, there are some indications of negative effects on human health or the environment, although the data basis is very thin due to the self regulation of the fragrance industry and the regulatory situation of fragrance substances. Third, many odoriferous substances used by man are identical to those which are signal substances of environmental organisms at very low concentrations, thus giving rise to specific mode of actions in the ecosystem. Recommendations For the adequate risk assessments of fragrances, test results on their unspecific as well as their specific effects as signal substances are needed. This would imply prioritisation methods and development of useful test methods for specific endpoints for appropriate risk assessments. Before a comprehensive testing and evaluation of results has been finished, a minimization of exposure should be envisaged. Eco-labelling of products containing acceptable fragrance ingredients could be a first step and provide consumers with the respective information. Transparency concerning the fragrance ingredients used and their biological potency will help to build up confidence between producers and consumers. Conclusions and Perspectives The interdisciplinary approach, bringing together chemical, biological, toxicological and ecotoxicological data with information provided by manufacturers and with legal and consumer aspects, offers new insights into the field of fragrance substances used in consumer products. The amounts and application fields of fragrance substances increases while fate and effects in the environment are hardly known. The current legal situation is not suited to elucidate the effects of fragrances on human health and the environment sufficiently, especially as it was shown that fragrances may play a considerable role in the ecosystem on the behaviour of organisms. According to the precautionary principle, the lack of knowledge should best be tackled by reducing exposure, especially for compounds such as fragrance substances where no ethical reasons object a substitution by less hazardous chemicals. ESS-Submission Editor: Dr. Thomas Knacker (th-knacker@ect.de)     

Effect of different soil types on the enchytraeids Enchytraeus albidus and Enchytraeus luxuriosus using the herbicide Phenmedipham

Soil ecotoxicology studies are usually performed in standard soils, such as the OECD (Organization for Economic Cooperation and Development) artificial soil or the LUFA St. 2.2, a natural soil. When assessing the toxic effects in the environment, soil properties are often different from those in standard soils, which might lead to a different exposure situation for the test species and, therefore, to a different evaluation of the risk of the test substance. Selected to cover a broad range of properties and based on the Euro-Soils concept, 18 different soils were studied regarding their suitability to two test species: Enchytraeus albidus and Enchytraeus luxuriosus (Enchytraeidae). In reproduction tests, the test species reacted differently to the tested soils, but both enchytraeids did not survive in acid soils (i.e. pH相似文献   

Analysis of Herbicide Krovar I™ by Liquid Chromatography with Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

A simple, very efficient method is presented for routine analysis of herbicide Krovar I? (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid–liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 µg L^?1 and for diuron 0.03 µg L^?1. Method detection limit for soil samples is 0.01 µg g^?1 dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Approach for extrapolating in vitro metabolism data to refine bioconcentration factor estimates

National and international chemical management programs are assessing thousands of chemicals for their persistence, bioaccumulative and environmental toxic properties; however, data for evaluating the bioaccumulation potential for fish are limited. Computer based models that account for the uptake and elimination processes that contribute to bioaccumulation may help to meet the need for reliable estimates. One critical elimination process of chemicals is metabolic transformation. It has been suggested that in vitro metabolic transformation tests using fish liver hepatocytes or S9 fractions can provide rapid and cost-effective measurements of fish metabolic potential, which could be used to refine bioconcentration factor (BCF) computer model estimates. Therefore, recent activity has focused on developing in vitro methods to measure metabolic transformation in cellular and subcellular fish liver fractions. A method to extrapolate in vitro test data to the whole body metabolic transformation rates is presented that could be used to refine BCF computer model estimates. This extrapolation approach is based on concepts used to determine the fate and distribution of drugs within the human body which have successfully supported the development of new pharmaceuticals for years. In addition, this approach has already been applied in physiologically-based toxicokinetic models for fish. The validity of the in vitro to in vivo extrapolation is illustrated using the rate of loss of parent chemical measured in two independent in vitro test systems: (1) subcellular enzymatic test using the trout liver S9 fraction, and (2) primary hepatocytes isolated from the common carp. The test chemicals evaluated have high quality in vivo BCF values and a range of logK(ow) from 3.5 to 6.7. The results show very good agreement between the measured BCF and estimated BCF values when the extrapolated whole body metabolism rates are included, thus suggesting that in vitro biotransformation data could effectively be used to reduce in vivo BCF testing and refine BCF model estimates. However, additional fish physiological data for parameterization and validation for a wider range of chemicals are needed.     

添加壳聚糖溶胶-凝胶法制备的TiO2光催化剂及其光催化性能研究

采用添加壳聚糖（CTS）的溶胶-凝胶法制备了具有较高光催化活性的TiO2光催化剂，并用XRD、TEM、BET和IR等手段对其进行表征。结果表明，CTS的添加使TiO2衍射强度增强、分散性提高、比表面积增大从而使光催化活性提高；用所制备的催化剂光催化降解甲基橙反应60min后，其去除率由不添加CTS所制备TiO2的32％提高到48％，TOC去除率由14％提高到23％。     

添加壳聚糖溶胶-凝胶法制备的TiO_2光催化剂及其光催化性能研究

采用添加壳聚糖(CTS)的溶胶-凝胶法制备了具有较高光催化活性的TiO_2光催化剂,并用XRD、TEM、BET和IR等手段对其进行表征。结果表明,CTS的添加使TiO_2衍射强度增强、分散性提高、比表面积增大从而使光催化活性提高;用所制备的催化剂光催化降解甲基橙反应60 min后,其去除率由不添加CTS所制备TiO_2的32%提高到48%,TOC去除率由14%提高到23%。     

Foliar washoff of pesticides (FWOP) model: Development and evaluation

Abstract

The Foliar Washoff of Pesticides (FWOP) Model was developed to provide an empirical simulation of pesticide washoff from plant leaf surfaces as influenced by rainfall amount. To evaluate the technique, simulations by the FWOP Model were compared to those by the foliar washoff algorithm of the Chemical, Runoff and Erosion from Agricultural Management Systems (CREAMS) Model. The two algorithms were linked individually to the Pesticide Runoff Simulator (PRS) for the comparison. Five years of test data from a Mississippi watershed were used to evaluate six insecticides (carbaryl, profenofos, methyl parathion, permethrin, phorate, and toxaphene).

Initially, the FWOP model was used to evaluate the relative impact of chemical distribution (foliage versus soil) on the subsequent foliar washoff and soil surface contributions to runoff losses. Results indicated that runoff losses were low If all of the insecticide was applied to the foliage whereas high losses occurred if applied only to the soil. When an assumed application was distributed between the plant and soil (i.e., 90% to foliage and 10% to soil), predicted runoff losses compared well with observed field data (<3% of the application rate).

Except for toxaphene, the FWOP model generally predicted less washoff and subsequent runoff losses than the CREAMS approach. Simulated toxaphene washoff losses were in good agreement with observed field data. Statistical comparisons of the two modeling approaches using the Kolmogorov‐Smirnov test showed differences in the two cumulative frequency distributions for washoff but smaller differences for runoff. Average 5‐year runoff losses, however, were greater using the CREAMS approach—by factors of 2, 3, and 3 for profenofos, methyl parathion and phorate, respectively.

Results from this study will be useful for upgrading current exposure assessment models to more accurately address foliar washoff losses of pesticides as well as for assessing the impact of foliar‐applied chemicals on environmental quality.     

Ozonation of azo dye Acid Red 14 in a microporous tube-in-tube microchannel reactor: decolorization and mechanism

Despite the great success of time-weighted average passive sampling of hydrophobic contaminants, such as PCBs and PAHs, the sampling of polar organic compounds still presents a challenge because the equilibrium between water and most sampling phases is attained in a relatively short time. In this study, we proposed a new time-integrative sampler using in situ solvent extraction (TISIS) for polar organic chemicals. The sampler was composed of a 15 cm poly(dimethylsiloxane) (PDMS) tubing, with an internal diameter of 0.5 mm and wall thickness of 0.5 mm, through which an extraction solvent (acetonitrile) was passed. Four polar organic contaminants, caffeine, atrazine, diuron and 17α-ethynylestradiol, were chosen for the evaluation of the performance of the sampler. Without the use of in situ solvent extraction, the PDMS tubing when exposed to a constant aqueous concentration of the four model compounds was able to linearly accumulate those compounds for less than 12 h and equilibrium between the PDMS tubing and water was attained in 2 d under our laboratory conditions. However, TISIS when exposed to a constant aqueous concentration was able to linearly accumulate all the model compounds without any exposure time limitation. The measured sampling rates at three different extraction flow rates (0.2, 0.5, 1.5 mL min⁻¹) were similar, regardless of the chemicals, indicating that the overall mass transfer from aqueous solution to the extraction solvent was most likely dominated by partitioning to the PDMS tubing and the internal diffusion within PDMS. In addition, a pulsed exposure experiment confirmed that TISIS operated in a time-integrative mode when the environmental concentration was highly fluctuated.     

The effects of ammonium sulphate and urea upon egg hatching and miracidial survival of Schistosoma mansoni

The effects of various concentrations of ammonium sulphate and urea on egg hatching and miracidial survival of S. mansoni were tested in order to determine if the use of these fertilizers in the ricelands of the Republic of Cameroon could affect the transmission of schistosomiasis. Results indicate that hatching of eggs and survival of miracidia varied with concentrations of tested chemicals and times of exposure. Exposure of S. mansoni eggs to 0.20%-1.00% ammonium sulphate or to 0.50%-4.00% urea reduced their ability to hatch and produce miracidia. A chemical concentration of 1.00% ammonium sulphate or 4.00% urea was found to be sufficient to produce complete inhibition of hatching. High concentrations of both chemicals not only inhibited miracidial emergence but also may be ovocidal. Results obtained from miracidial survival tests indicated that LC5, LC50 and LC95 values for ammonium sulphate were 0.07%, 0.80% and 10.61% after 2 hours of exposure; 0.03%, 0.16% and 0.90% after 4 hours of exposure; and 0.30%, 0.20% and 0.40% after 6 hours of exposure respectively. Similar statistical analyses revealed that the LC5, LC50 and LC95 values for urea were 0.22%, 1.90% and 16.25% after 2 hours of exposure; 0.28%, 0.57% and 1.14% after 4 hours of exposure; and 0.13%, 0.27% and 0.57% after 6 hours of exposure respectively. Although the two fertilizers exerted some adverse effects on S. mansoni eggs and miracidia at relatively high concentrations, neither of them was found to be of practical value. Ammonium sulphate and urea concentrations effective in killing S. mansoni eggs and miracidia were about one to two orders of magnitude greater than the actual field application rates.     

Environmental and biological monitoring of endocrine disrupting chemicals.

Trends toward an increase of adverse health effects on reproductive organs have been reviewed. An urgent need has been recognised to establish validated in vivo and in vitro screening assays to test for hormonal activities of chemicals. Relevant existing OECD guidelines have been reviewed and enhancements of some of these have been identified, mainly to test for estrogenic and androgenic activity of chemicals. The problems connected to monitoring activities are outlined, particularly for ambient and biological monitoring. Indeed, the problem of assessing human exposure to endocrine disrupting chemicals through environmental chemical analysis tends to a very high level of complexity. This has been illustrated through the example of one single subclass of endocrine disrupting compounds (EDCs), the organohalogen compounds. Valid biological markers are also needed to be effectively used in epidemiological studies and risk assessment. A multidisciplinary approach and the collaboration among experts in the field of clinical biochemistry, toxicology, and epidemiology is required.