Temperature and Concentration Effects in Biomonitoring of Organic Air Pollutants

Up to now only very few studies in biomonitoring of organic air pollutants have been published taking into account the strong influence mean temperatures have on the accumulation process into plants during the course of the exposition. Temperature governed sorption as well as the plants vitality pose a major source of uncertainty making inter-study comparisons difficult. Different surface-to-volume ratios of plant foliage lead to strongly varying concentration effects in different plant species. Moreover a plants content of waxes and lipids must be considered in order to relate xenobiotic concentrations to the compounds being most efficient in the bioaccumulation process. Some of these factors are evaluated in regard to the use of plants as biomonitors for organic air pollutants. Another aim is to deduce the mean ambient gas phase concentrations from PAH concentrations determined in the biomonitor plants using vegetation-air partitioning coefficients which have been corrected for temperature dependent sorption as well as the plants lipid content. Restrictions of such approaches and methods of biomonitoring in general are discussed.     

The effects of scale and spatial heterogeneities on diffusion in volcanic breccias and basalts: Amchitka Island, Alaska

Knowledge of the factors that influence the diffusion of contaminants, such as the diffusivity and the connected porosity, is crucial to modeling the long-term fate and transport of contaminants in subsurface systems with small or negligible advective flow, such as in fractured crystalline rock. Fractured rock is naturally heterogeneous, and hence, understanding the diffusivity of a molecule through this material (or the formation factor of the medium) becomes a complex problem, with critical concerns about the scale of laboratory measurements and about the spatial variability of these measurements relative to the scale needed for fate and transport modeling. This study employed both electrical and tracer-based laboratory methods to investigate the effects of scale and pore system connectivity on the diffusivity for volcanic matrix rock derived from the study site, a former underground nuclear test site at Amchitka Island, Alaska. The results of these investigations indicate a relatively well-connected pore system with scale effects generally limited to approximately 6 cm lengths and well-correlated to observed heterogeneous features. An important conclusion resulting from this study, however, is that there is a potential for the estimated diffusivity to be misrepresented by an order of magnitude if multiple samples or longer sample lengths are not used. Given the relatively large number of measurements resulting from these investigations, an analysis of the probability density function (PDF) of the diffusivity was possible. The PDF of the diffusivity was shown to generally follow a normal distribution for individual geologic layers. However, when all of the geologic layers are considered together, the distribution of the subsurface as a whole was shown to follow a lognormal distribution due to the order of magnitude differences amongst the layers. An understanding of these distributions is essential for future stochastic modeling efforts.     

Evaluation of effects of exposure time on aquatic toxicity with zooplanktons using a reduced life expectancy model

Traditionally in toxicological studies time is not studied as quantifiable variable but as a fixed endpoint. The Reduced Life Expectancy (RLE) model which relates exposure time and exposure concentration with lethal toxic effects was tested previously using fish data. In this current paper the effects of exposure time on aquatic toxicity with zooplanktons and various toxicants were evaluated using the RLE model based on ambient exposure concentration. The model was evaluated by plotting ln LT₅₀ against LC₅₀ using toxicity data with zooplanktons from the literature for metal, metalloid and organic compounds. Most of the experimental data sets can be satisfactorily correlated by use of the RLE model, but deviations occurred for some data sets. Those data sets were satisfactorily fitted by a two stage RLE model. This model was based on two phases: one in the peripheral system and other in the central system. Both the single and two stage RLE model support the hypothesis that toxicity is time dependent and decreases in a systematic way with increasing exposure time. A calculated normal life expectancy (NLT) can be obtained from the single stage model and is in accord with reported NLT but those obtained from the two stage RLE model are in excellent agreement.     

Endpoint ‘floating leaves’ of <Emphasis Type="Italic">Potamogeton natans</Emphasis>: A new method to evaluate the development of macrophytes in pond mesocosms

Goal, Scope and Background One of the advantages of long-term mesocosm experiments as compared to short-term standard toxicity tests in the laboratory is the potential for detecting secondary effects due to the interaction of species and recovery with biomass of macrophytes being an important endpoint. However, generating biomass data by harvesting is often laborious, time-consuming, costly and restricted to the end of the experiment. Moreover, valuable information may get lost, in particular in single application studies, since maximal primary effects and secondary effects or recovery occur per se at different times. Potamogeton natans was used as an example in order to test whether number and area of floating leaves can be reliably measured and be used as intermediate and final endpoints in mesocosm effect studies. Methods Digital photos, which were taken of the water surface in the course of an indoor pond mesocosm study on herbicide effects, were subjected to image analysis. The results were compared to wet weight and ash-free dry weight of Potamogeton at the end of the herbicide study. Results and Discussion Both number and area of floating leaves indicated the same herbicide effects as wet weight and ash-free dry weight of Potamogeton. Error introduced by the different work steps is small and can be further minimised by a number of method improvements. Recommendations and Perspectives In indoor mesocosm studies, errors due to the perspective adjustment may be circumvented by taking the photos perpendicular to the water surface. Correction for lens aberration, identical light conditions and the use of fluorescence images are considered promising. Field applications are proposed.     

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)     

三峡大坝对重庆城区水环境的影响及对策

本文在假定城区排污量维持1990年水平的条件下,用计算机模拟了三峡大坝建成后重庆城区长江、嘉陵江岸边污染带增宽的情况。同时,借助水质模型模拟的2000年时城区的水质状况和城区两个控制断面上的多年监测浓度值,用灰色理论预测了三峡水库形成后重庆城区的实际岸边污染带宽度和九种污染物的断面平均浓度。最后,提出一套最佳的对策方案及投资估算。     

有色金属冶炼区铊(Tl)的水环境分布特征与环境对策--以大冶冶炼厂地区的东岗河为例

以大冶冶炼厂地区的东岗河为例,分析有色金属冶炼区铊的水环境分布特征,结果表明：河水中的铊含量明显异常(严重污染区的平均含量为15．07ng／mL。远超过饮用水源水中铊的最高允许浓度0．1ng／mL)．且与水体pH值、Cu^2 、Pb^2 等含量显著相关;铊与Pb等亲铜元素呈类质同像。宏观上与方铅矿、闪锌矿、黄铁矿、黄铜矿等伴生．因此后者成为研究区铊的重要来源。最后,对铊所造成的环境危害效应．提出相应的解决对策,并提醒人们提高对铊污染的警惕性以及加深对铊的研究。     

Carbonate-induced enhancement of phenols degradation in CuS/peroxymonosulfate system: A clear correlation between this enhancement and electronic effects of phenols substituents

This study investigated the enhancement effects of dissolved carbonates on the peroxymonosulfate-based advanced oxidation process with CuS as a catalyst. It was found that the added CO₃²⁻ increased both the catalytic activity and the stability of the catalyst. Under optimized reaction conditions in the presence of CO₃²⁻, the degradation removal of 4-methylphenol (4-MP) within 2 min reached 100%, and this was maintained in consecutive multi-cycle experiments. The degradation rate constant of 4-MP was 2.159 min⁻¹, being 685% greater than that in the absence of CO₃²⁻ (0.315 min⁻¹). The comparison of dominated active species and 4-MP degradation pathways in both CO₃²⁻-free and CO₃²⁻-containing systems suggested that more CO₃•⁻/¹O₂ was produced in the case of CO₃²⁻deducing an electron transfer medium, which tending to react with electron-rich moieties. Meanwhile, Characterization by X-ray photoelectron spectroscopic and cyclic voltammetry measurement verified CO₃²⁻ enabled the effective reduction of Cu²⁺ to Cu⁺. By investigating the degradation of 11 phenolics with different substituents, the dependence of degradation kinetic rate constant of the phenolics on their chemical structures indicated that there was a good linear relationship between the Hammett constants σ_p of the aromatic phenolics and the logarithm of k in the CO₃²⁻-containing system. This work provides a new strategy for efficient removal of electron-rich moieties under the driving of carbonate being widely present in actual water bodies.     

苦味酸测定中关键问题的研究

目前测定苦味酸的国标方法为《生活饮用水标准检验方法有机物指标》(GB/T 5750.8—2006)中的衍生物-液液萃取-气相色谱法,在实际测试过程中,发现水样pH值和基质效应会影响苦味酸测定。当pH值为8~12时,生成的氯化苦响应强度变化不大;在pH约为13时,响应强度最大。水质中除腐殖酸、硝基甲烷及2,4,6-三硝基甲苯会影响苦味酸测定外,硝基酚类和甲基酚类同样起到正干扰作用,因此,国标方法不能全面和准确地测定水中的苦味酸含量。     

Phytotoxicity of atrazine, isoproturon, and diuron to submersed macrophytes in outdoor mesocosms

The submersed macrophytes Elodea canadensis, Myriophyllum spicatum and Potamogeton lucens were constantly exposed over a five-week period to environmentally relevant concentrations of atrazine, isoproturon, diuron, and their mixture in outdoor mesocosms. Effects were evaluated investigating photosynthetic efficiency (PE) of the three macrophytes and growth of M. spicatum and E. canadensis. Adverse effects on PE were observed on days 2 and 5 after application. M. spicatum was found to be the more sensitive macrophyte. E. canadensis and P. lucens were less sensitive to atrazine, diuron and the mixture and insensitive to isoproturon. PE of M. spicatum was similarly affected by the single herbicides and the mixture demonstrating concentration addition. Growth of E. canadensis and M. spicatum was not reduced indicating that herbicide exposure did not impair plant development. Although PE measurements turned out to be a sensitive method to monitor PSII herbicides, plant growth remains the more relevant ecological endpoint in risk assessment.