Extended geometric method: a simple approach to derive adsorption rate constants of Langmuir-Freundlich kinetics

A new and simple equation has been presented here for calculation of adsorption and desorption rate constants of Langmuir-Freundlich kinetic equation. The derivation of new equation is on the basis of extension and correction to the geometric method which has been presented by Kuan et al. [Kuan, W.-H., Lo, S.-L., Chang, C.M., Wang, M.K., 2000. A geometric approach to determine adsorption and desorption kinetic constants. Chemosphere 41, 1741-1747] for the kinetics of adsorption/desorption in aqueous solutions. The correction is to consider that the concentration of solute is not constant and changes as adsorption proceeds. The extension is that we applied Langmuir-Freundlich kinetic model instead of Langmuir kinetic model to consider the heterogeneity and therefore it is more applicable to the real systems. For solving Langmuir-Freundlich kinetic model, some geometric methods and also Taylor expansion were used and finally a simple and novel equation was derived (Eq. (20)) for calculation of adsorption rate constant. This new method was named "extended geometric method". The input data of the obtained equation can be simply derived from initial data of adsorption kinetics. Finally the adsorption of methyl orange onto granular activated carbon was carried out at dynamic and equilibrium conditions and the capabilities of extended geometric method were examined by the experimental data.     

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)     

Characteristics and driving factors of marsh changes in Zhalong wetland of China

Zhalong National Nature Reserve in the northeast of China is a large wetland and a habitat of hundreds species of fauna and flora. The rare red-crowned crane is one kind of endangered birds in it. Recently, Zhalong wetland is shrinking and it encounters many problems including occasional fires, bad water quality, human activities, etc. In order to find out a proper way to protect and restore the wetland, this study, using a geographic information system, the global positioning system and remote sensing techniques, analyses the spatial characteristics of the changes in marsh landscape pattern and examines the driving factors for these changes. Data sources include 8 Landsat Thematic Mapper satellite images of Zhalong area in the period of 1986–2002 and the investigation information on site. Based on the analysis of changes of marsh area and annual precipitation during the 16 years, it is found that there is a close correlation between annual precipitation and marsh area. It means that climate is one of driving factors of marsh pattern changes. To understand influences of other kinds of land uses on marsh spatial distribution in Zhalong wetland, this paper analyses the relationship between marsh and different kinds of land uses, such as water surface, residential area, farmland, salina land and grass land, respectively. According to the patch analysis theory, a fragmental index and a fractal dimension of the marsh are calculated with perimeter-area method. The results indicate that the marsh pattern is affected by human activities significantly. In addition, the location alteration of marsh centroid point over the 16 years is studied. The movement trace of marsh centroid point is concerned with different hydrological situation in different areas of the wetland. In summary the characteristics of the marsh landscape pattern evolution during the 16 years are affected by multiple driving factors. The main driving factors are climate, human activities, distribution of other kinds of land uses and hydrological situation in different areas.     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

A Procedure for NEPA Assessment of Selenium Hazards Associated With Mining

This paper gives step-by-step instructions for assessing aquatic selenium hazards associated with mining. The procedure was developed to provide the U.S. Forest Service with a proactive capability for determining the risk of selenium pollution when it reviews mine permit applications in accordance with the National Environmental Policy Act (NEPA). The procedural framework is constructed in a decision-tree format in order to guide users through the various steps, provide a logical sequence for completing individual tasks, and identify key decision points. There are five major components designed to gather information on operational parameters of the proposed mine as well as key aspects of the physical, chemical, and biological environment surrounding it — geological assessment, mine operation assessment, hydrological assessment, biological assessment, and hazard assessment. Validation tests conducted at three mines where selenium pollution has occurred confirmed that the procedure will accurately predict ecological risks. In each case, it correctly identified and quantified selenium hazard, and indicated the steps needed to reduce this hazard to an acceptable level. By utilizing the procedure, NEPA workers can be confident in their ability to understand the risk of aquatic selenium pollution and take appropriate action. Although the procedure was developed for the Forest Service it should also be useful to other federal land management agencies that conduct NEPA assessments, as well as regulatory agencies responsible for issuing coal mining permits under the authority of the Surface Mining Control and Reclamation Act (SMCRA) and associated Section 401 water quality certification under the Clean Water Act. Mining companies will also benefit from the application of this procedure because priority selenium sources can be identified in relation to specific mine operating parameters. The procedure will reveal the point(s) at which there is a need to modify operating conditions to meet environmental quality goals. By recognizing concerns early in the NEPA process, it may be possible for a mining company to match operational parameters with environmental requirements, thereby increasing the likelihood that the permit application will be approved.     

Physicochemical substance properties as indicators for unreliable exposure in microplate-based bioassays

In the last years many efforts were made to transform standardized algal test protocols into low-cost microplate assays. While advantages were pointed out frequently, limitations are not systematically addressed, thus hindering a widespread utilisation. In this study a group of organic substances with a wide distribution of volatility (log K_AW from −6.53 to −2.13) and lipophilicity (log K_OW from 1.26 to 4.92) was investigated with respect to the influence of these physicochemical properties on their algal toxicity in different assays. Therefore the EC₅₀ values were determined with a microplate assay based on ISO 8692 protocol and the results were compared with those of an established algal growth inhibition test conducted in air tight glass vessels. Using the ratio of the EC₅₀ values, a clear connection between biological response and volatility as well as lipophilicity of test substances could be detected. Chemicals with a log K_OW higher than 3 or a Henry coefficient log K_AW higher than −4 were identified as less effective in the microplate assay than in the comparative assay. The loss in nominal concentration due to physicochemical properties could be shown to contribute to this using HPLC analysis. Consequently, when using microplate assay’s one should be aware that lipophilic and volatile chemicals might be underestimated in their toxicity, which could be indicated from evaluating related physicochemical properties modelled from structural information prior to an experimental investigation.     

Rapid humanitarian assessments and rationality: a value-of-information study from Iraq, 2003-04

Rapid assessments are one of the standard informational tools in humanitarian response and are supposed to contribute to rational decision-making.(1) The extent to which the assessment organisation itself behaves rationally, however, is an open question. This can be evaluated against multiple criteria, such as the cost and value of the information it collects and its ability to adapt flexibly design or samples when the survey environment changes unforeseeably. An unusual data constellation from two concurrent recent (2003-04) rapid assessments in northern Iraq permits us to model part of the actual assessment behaviour in terms of geographical, community and prior substantive information attributes. The model correctly predicts the decisions, in 79 per cent of the 2,425 local communities in focus, that data collector teams in the Emergency Mine Action Survey made to visit or not to visit. The analysis demonstrates variably rational behaviour under conditions of insecurity, repeated regrouping and incomplete sampling frames. A pronounced bias towards very small rural settlements is irrational for the overall results, but may be a rational strategy of individual survey workers seeking to prolong their employment. Implications for future assessments are sketched in the areas of tools for urban surveys, greater adaptability, including early feedback from users, and sensibility to value-of-information concepts.     

Review of the effects of in-stream pipeline crossing construction on aquatic ecosystems and examination of Canadian methodologies for impact assessment

Pipeline crossing construction alters river and stream channels, hence may have detrimental effects on aquatic ecosystems. This review examines the effects of crossing construction on fish and fish habitat in rivers and streams, and recommends an approach to monitoring and assessment of impacts associated with these activities. Pipeline crossing construction is shown to not only compromise the integrity of the physical and chemical nature of fish habitat, but also to affect biological habitat (e.g., benthic invertebrates and invertebrate drift), and fish behavior and physiology. Indicators of effect include: water quality (total suspended solids TSS), physical habitat (substrate particle size, channel morphology), benthic invertebrate community structure and drift (abundance, species composition, diversity, standing crop), and fish behavior and physiology (hierarchy, feeding, respiration rate, loss of equilibrium, blood hematocrit and leukocrit levels, heart rate and stroke volume). The Before-After-Control-Impact (BACI) approach, which is often applied in Environmental Effects Monitoring (EEM), is recommended as a basis for impact assessment, as is consideration of site-specific sensitivities, assessment of significance, and cumulative effects.     

Comparison of China’s Environmental Impact Assessment (EIA) Law with the European Union (EU) EIA Directive

In this paper, we first review the development of China’s Environmental Impact Assessment (EIA) system in the past 30 years. Then we compare the framework and operational procedures of China’s new EIA law with those of the EU EIA Directive. We also compare public participation, as well as sanctions and control in the two EIA systems. In addition, we identify where the processes in both EIA systems are similar or different from one another. By comparison, we noted that there are at least three obvious weaknesses in China’s EIA system: (1) the application of new models for EIA legislation; (2) the improvement of EIA guidance and education; and (3) the enhancement of public participation in EIA process. Our study indicates that these three major shortcomings should be overcome and improved in China’s EIA system, when compared with the EU EIA system.     

Real time remote monitoring of air pollutants and their online transmission to the web using internet protocol

Recent advances in both information and sensor technologies have enabled the development of Real Time Remote Monitoring (RTRM) capabilities for environmental management. An online and real time remote monitoring system for air pollution has been designed and installed at a traffic police station at Punjagutta in Hyderabad, India. The system is optimized using electrochemical sensors and a real time particulate matter analyzer. The system also monitors meteorological parameters such as temperature, humidity, rainfall, barometric pressure, wind speed and wind direction. The system periodically monitors both pollution and meteorological parameters at pre- programmed intervals of hr during peak periods and 1 hr during non peak periods of the day and continuously uploads to a predestinated web site (www.appcb.org/home.htm) using File Transfer Protocol. The web site renders a quick, simple and graphical display of air pollution levels and meteorological parameters and their significance to humans. The present paper highlights design considerations of a pollution monitoring system, system hardware and software requirements and practical limitations and future directions for real time remote monitoring of air pollution.