New risk assessment approach for systemic insecticides: the case of honey bees and imidacloprid (Gaucho)

The procedure to assess the risk posed by systemic insecticides to honey bees follows the European Directives and depends on the determination of the Hazard Quotient (HQ), though this parameter is not adapted to these molecules. This paper describes a new approach to assess more specifically the risk posed by systemic insecticides to honey bees with the example of imidacloprid (Gaucho). This approach is based on the new and existing chemical substances Directive in which levels of exposure (PEC, Predicted Exposure Concentration) and toxicity (PNEC, Predicted No Effect Concentration) are compared. PECs are determined for different categories of honey bees in relation to the amounts of contaminated pollen and nectar they might consume. PNECs are calculated from data on acute, chronic, and sublethal toxicities of imidacloprid to honey bees, to which selected assessment factors are applied. Results highlight a risk for all categories of honey bees, in particular for hive bees. These data are discussed in the light of field observations made on honey bee mortalities and disappearances. New perspectives are given to better determine the risk posed by systemic insecticides to honey bees.     

Landscape-level approach to assess aquatic exposure via spray drift for pesticides: a case study in a Mediterranean area

The development of methods to extract information from landscape analysis to refine risk assessment is becoming increasingly important. This paper presents results from a pesticide surface water exposure assessment at the watershed scale, based on a combination of edge of field studies, large-scale monitoring studies, and modeling activities with GIS-based landscape analysis methodologies covering an area of approximately 3200 ha surrounding the Simeto River in Sicily (Italy). The dynamic behavior of the pesticide chlorpyrifos-methyl was modeled in two different steps: calculation of the fraction of the application rate that is deposited beyond the field edge and simulation of the fate and persistence of the pesticide in the aquatic environment. Drift loads showed high spatial variability. Considering spray drift deposition as a fraction of the pesticide application rate, 60% of the results were < or = 0.02 (equal to 0.04 mg/m2). Only 8.5% of the results were above 0.5. The highly variability of the landscape factors was reflected in the results. More than 60% of the predicted pesticide concentrations were less than the limit of quantification (0.05 microg/L), affecting about 75% of the total length of the river tract analyzed. Predicted pesticide concentrations were higher than 0.1 microg/L in 23% of cases, but this corresponded to an insignificant portion of the river (1.2% of the total length). These results suggest that management options, such as increased no-spray zones, could provide further protection for surface water. These could be modeled to illustrate their overall impact. As an alternative, the introduction of a 20-m no-spray zone clearly reduced potential exposure, and 92% of the water body was protected. Estimated data are in agreement with data collected during a field monitoring study.     

Benchmark and strategy development for microbial fuel cells in industrial wastewater treatment

The chemical energy hidden in wastewater can be extracted, turning an energy-intensive treatment process into an energy-independent one. However, conventional aerobic treat- ment is very energy intensive, and anaerobic treatment requires a post-treatment step to meet stringent discharge requirements. Therefore, Microbial Fuel Cells (MFCs) have attracted a lot of attention because of their ability to extract electrical energy directly from wastewater during the treatment process. Since combustion losses can be avoided, theoretically the greatest energy value can be obtained from the organic load. However, most MFC research is currently still taking place on a laboratory scale in the treatment of synthetic or municipal wastewater. Commercialization of MFC technology will require large-scale plants, for which a suitable MFC design and operation concepts must first be identified, since neither configuration nor operating system has been clearly established yet. In addition, no specific concepts and application fields currently exist for the treat- ment of industrial wastewater. Consequently, with regard to MFCs in industrial wastewater treatment, the aim of this work is to develop a benchmark that serves for modeling the required overall efficiency of MFCs and to identify the most relevant key factors in order to derive enhancement strate- gies. By providing an overview of current MFCs in industrial wastewater treatment and developing a benchmark, the targets for long-term operation of MFCs can be established allowing critical factors for design and operation to be identified. The resulting enhance- ment strategies were validated and the overall evaluation with the developed benchmark allowed an assessment regarding the commercialization potential. Compared to the first MFC design (MFC 1.0), the enhanced MFC design (MFC 2.0) increased the power density by a factor of up to 11 and extended the long-term stability to one year by increasing the specific cathode surface area and reducing the electrode spacing in conjunction with avoiding fiber clogging on the anode side. In addition to using beneficial brewery wastewater with high content of easily degradable organic acids and high conductivity, the performance of the MFC was further stabilized and improved by changing the operating mode to continuous operation and reducing the hydraulic re- tention time to 6 h, resulting in a mean organic removal rate of 6.5 ± 1.9 kg/(m³ · d). Although the overall energy efficiency is low compared to anaerobic treatment, the enor- mous wastewater treatment potential forms the basis for MFCs to become an alternative to conventional treatment technologies if self-sufficient treatment is targeted. Due to the wide range of operating conditions and the modularity of stack systems, MFCs can become a promising option especially for industrial wastewater treatment.     

离子对壳聚糖/果胶聚电解质复合物溶胀性及微观结构的影响研究

本文将壳聚糖、果胶在含有六种不同离子的溶液环境中复合,考察离子种类及浓度对壳聚糖/果胶聚电解质复合物（PEC）得率、溶胀度（水及模拟环境中）、红外光谱及微观结构的影响。离子价态对PEC得率的影响为：三价离子〉二价离子〉一价离子;离子浓度低时,离子浓度促进PEC得率增加,离子浓度高时,离子浓度抑制PEC得率增加。离子种类不同,PEC的溶胀过程不同,复合环境中含有FeCl3和Fe2（SO4）3的PEC在水中具有最大、最小溶胀度,分别为56.87±0.63和9.21±0.13;含有MgSO4和Fe2（SO4）3的PEC在胃肠模拟液中具有最大、最小溶胀度,分别为361.74±6.21和28.01±0.66。红外光谱结果表明添加离子并未影响PEC中NH3＋/COO-键的形成。扫描电镜结果显示PEC呈海绵多孔状,添加离子后PEC孔壁厚度增加9.76±1.03%至334.19±5.12%不等,表面更加光滑,而孔隙状态因离子种类不同而不同。研究表明PEC得率、溶胀度及微观结构受到离子影响,但其交联方式不变。     

Relationships between soil organic matter, nutrients, bacterial community structure, and the performance of microbial fuel cells

Microbial fuel cells (MFCs) offer the potential for generating electricity, mitigating greenhouse gas emissions, and bioremediating pollutants through utilization of a plentiful renewable resource: soil organic carbon. We analyzed bacterial community structure, MFC performance, and soil characteristics in different microhabitats within MFCs constructed from agricultural or forest soils in order to determine how soil type and bacterial dynamics influence MFC performance. Our results indicated that MFCs constructed from agricultural soil had power output about 17 times that of forest soil-based MFCs and respiration rates about 10 times higher than forest soil MFCs. Agricultural soil MFCs had lower C:N ratios, polyphenol content, and acetate concentrations than forest soil MFCs. Bacterial community profile data indicate that the bacterial communities at the anode of the high power MFCs were less diverse than in low power MFCs and were dominated by Deltaproteobacteria, Geobacter, and to a lesser extent, Clostridia, while low-power MFC anode communities were dominated by Clostridia. These results suggest that the presence of organic carbon substrate (acetate) was not the major limiting factor in selecting for highly electrogenic bacterial communities, while the quality of available organic matter may have played a significant role in supporting high performing bacterial communities.     

Temporal changes in surface-water insecticide concentrations after the phaseout of diazinon and chlorpyrifos

The recent (late 2001) federally mandated phaseout of diazinon and chlorpyrifos insecticide use in outdoor urban settings has resulted in a rapid decline in concentrations of these insecticides in urban streams and rivers in the northeastern and midwestern United States. Assessment of temporal insecticide trends at 20 sites showed that significant step decreases in diazinon concentrations occurred at 90% of the sites after the phaseout, with concentrations generally decreasing by over 50% in summer samples. Chlorpyrifos concentrations showed significant step decreases in at least 1 season at 3 of the 4 sites with sufficient data for analysis. The decrease in diazinon concentrations in response to the phaseout resulted in a decline in the frequency of concentrations exceeding the acute invertebrate water-quality benchmark of 0.1 microg/L from 10% of pre-phaseout summer samples to fewer than 1% of post-phaseout summer samples. Although some studies have indicated an increase in concentrations of carbaryl in response to the organophosphorous phaseout, carbaryl concentrations only increased at 1 site after the phaseout. A full assessment of the effect of the phaseout of diazinon and chlorpyrifos on surface water will require data on other insecticides used to replace these compounds.     

三种离子物质对壳聚糖/果胶聚电解质复合物牛血清蛋白释放特性的影响

分别添加氯化钠、硫酸钠、氯化铁制备壳聚糖/果胶聚电解质复合物(PEC),研究其对牛血清蛋白(BSA)的负载能力及模拟释放行为,以探讨三种离子物质对壳聚糖/果胶PEC在蛋白缓释方面的影响。氯化铁PEC对BSA的包埋率最大,其次为硫酸钠、氯化钠,载药率为氯化钠PEC最大、其次为硫酸钠、氯化铁。在单一模拟环境中,各PEC在模拟胃液中的BSA累积释放率最小,在模拟结肠液中最大;氯化钠会使PEC的BSA释放率降低,而硫酸钠与氯化铁则可增大蛋白释放率;各PEC的蛋白释放行为属于Fick扩散。在连续模拟环境中,模拟胃液中BSA累积释放率较低,在模拟肠道环境中BSA大量释放,含有氯化钠的PEC累积释放率最低;在模拟结肠液中含有果胶酶时,各PEC的BSA累积释放率可达98%以上;各PEC的蛋白释放动力学属于非Fick扩散。含有三种离子物质的壳聚糖/果胶PEC均具有良好的p H敏感性和定点释放特性。     

Microbial fuel cells: methodology and technology

Microbial fuel cell (MFC) research is a rapidly evolving field that lacks established terminology and methods for the analysis of system performance. This makes it difficult for researchers to compare devices on an equivalent basis. The construction and analysis of MFCs requires knowledge of different scientific and engineering fields, ranging from microbiology and electrochemistry to materials and environmental engineering. Describing MFC systems therefore involves an understanding of these different scientific and engineering principles. In this paper, we provide a review of the different materials and methods used to construct MFCs, techniques used to analyze system performance, and recommendations on what information to include in MFC studies and the most useful ways to present results.     

Effects of membrane cation transport on pH and microbial fuel cell performance

Due to the excellent proton conductivity of Nafion membranes in polymer electrolyte membrane fuel cells (PEMFCs), Nafion has been applied also in microbial fuel cells (MFCs). In literature, however, application of Nafion in MFCs has been associated with operational problems. Nafion transports cation species other than protons as well, and in MFCs concentrations of other cation species (Na+, K+, NH4+, Ca2+, and Mg2+) are typically 10(5) times higher than the proton concentration. The objective of this study, therefore, was to quantify membrane cation transport in an operating MFC and to evaluate the consequences of this transport for MFC application on wastewaters. We observed that during operation of an MFC mainly cation species other than protons were responsible for the transport of positive charge through the membrane, which resulted in accumulation of these cations and in increased conductivity in the cathode chamber. Furthermore, protons are consumed in the cathode reaction and, consequently, transport of cation species other than protons resulted in an increased pH in the cathode chamber and a decreased MFC performance. Membrane cation transport, therefore, needs to be considered in the development of future MFC systems.     

Autotrophic denitrification in microbial fuel cells treating low ionic strength waters

The presence of elevated concentrations of nitrates in drinking water has become a serious concern worldwide. The use of autotrophic denitrification in microbial fuel cells (MFCs) for waters with low ionic strengths (i.e., 1000 μS·cm(-1)) has not been considered previously. This study evaluated the feasibility of MFC technology for water denitification and also identified and quantified potential energy losses that result from their usage. The low conductivity (<1600 μS·cm(-1)) of water limited the nitrogen removal efficiency and power production of MFCs and led to the incomplete reduction of nitrate and the nitrous oxide (N(2)O) production (between 4 and 20% of nitrogen removed). Cathodic overpotential was identified as the main energy loss factors (83-90% of total losses). That high overpotential was influenced by denitrification intermediates (NO(2)(-) and N(2)O) and the potential used by microorganisms for growth, activation, and maintenance.     

Electricity generation using an air-cathode single chamber microbial fuel cell in the presence and absence of a proton exchange membrane

Microbial fuel cells (MFCs) are typically designed as a two-chamber system with the bacteria in the anode chamber separated from the cathode chamber by a polymeric proton exchange membrane (PEM). Most MFCs use aqueous cathodes where water is bubbled with air to provide dissolved oxygen to electrode. To increase energy output and reduce the cost of MFCs, we examined power generation in an air-cathode MFC containing carbon electrodes in the presence and absence of a polymeric proton exchange membrane (PEM). Bacteria present in domestic wastewater were used as the biocatalyst, and glucose and wastewater were tested as substrates. Power density was found to be much greater than typically reported for aqueous-cathode MFCs, reaching a maximum of 262 +/- 10 mW/m2 (6.6 +/- 0.3 mW/L; liquid volume) using glucose. Removing the PEM increased the maximum power density to 494 +/- 21 mW/m2 (12.5 +/- 0.5 mW/L). Coulombic efficiency was 40-55% with the PEM and 9-12% with the PEM removed, indicating substantial oxygen diffusion into the anode chamber in the absence of the PEM. Power output increased with glucose concentration according to saturation-type kinetics, with a half saturation constant of 79 mg/L with the PEM-MFC and 103 mg/L in the MFC without a PEM (1000 omega resistor). Similar results on the effect of the PEM on power density were found using wastewater, where 28 +/- 3 mW/m2 (0.7 +/- 0.1 mW/L) (28% Coulombic efficiency) was produced with the PEM, and 146 +/- 8 mW/m2 (3.7 +/- 0.2 mW/L) (20% Coulombic efficiency) was produced when the PEM was removed. The increase in power output when a PEM was removed was attributed to a higher cathode potential as shown by an increase in the open circuit potential. An analysis based on available anode surface area and maximum bacterial growth rates suggests that mediatorless MFCs may have an upper order-of-magnitude limit in power density of 10(3) mW/m2. A cost-effective approach to achieving power densities in this range will likely require systems that do not contain a polymeric PEM in the MFC and systems based on direct oxygen transfer to a carbon cathode.     

GIS-based system for surface water risk assessment of agricultural chemicals. 1. Methodological approach

A methodology to develop a GIS-based system for the surface water risk assessment of agricultural chemicals is described. It is based on the integration of relational and spatial databases, GIS incorporating raster and vector, mass balance models, and pesticide risks indicators. Surface water pollution was modeled by taking into account two main processes: the load due to drift and the load due to a rainfall-runoff event. The former is immediately consequent to pesticide application; the second occurs a short period afterward. Thus two distinct PEC (predicted environmental concentration) values were estimated, differing in time. A pilot approach was applied to the herbicide alachlor on corn in Lombardia region (northern Italy) and represents the first stage of a wider project. Although the resultant alachlor PEC and risk maps represent a static image of a worst-case simulation, the main objective was to provide information for the territory with respect to relative risks at the watershed level, which is important in managing risks to the aquatic environment. The driving forces and spatial variability of the above-mentioned processes were investigated to improve knowledge about the territory and to indicate the need for more detailed site-specific studies.     

Including transformation products into the risk assessment for chemicals: the case of nonylphenol ethoxylate usage in Switzerland

A method for applying the risk assessment approach using ratios of predicted environmental concentrations (PECs) and predicted no-effect concentrations (PNECs) to mixtures of parent compounds and their environmental transformation products is presented. Nonylphenol ethoxylates (NPnEOs) and a selection of their most relevant transformation products are investigated as a case study illustrating the method. The PEC values of NPnEO and its transformation products are calculated with a regional multimedia fate model including the transformation kinetics of the NPnEO degradation cascade. PNEC values are derived from a selection of toxicity data on NPnEO and its transformation products. The toxicity of the emerging mixture of NPnEO and its transformation products is then estimated under the assumption of concentration addition (similar mode of action). On this basis, PEC-to-PNEC ratios for the aquatic environment and the sediment are calculated for the individual components of the mixture and the mixture itself. For this purpose, average release rates of NPnEO and its transformation products from Swiss sewage treatment plants were used. While the PEC values of the individual components do not exceed the corresponding PNEC values, the risk quotient of the mixture in water is greater than 1. In sediment, the mixture does not exceed a risk quotient of 1. A combination of sensitivity and scenario analyses is employed to identify the upper and lower bounds of the results.     

Cathode performance as a factor in electricity generation in microbial fuel cells

Although microbial fuel cells (MFCs) generate much lower power densities than hydrogen fuel cells, the characteristics of the cathode can also substantially affect electricity generation. Cathodes used for MFCs are often either Pt-coated carbon electrodes immersed in water that use dissolved oxygen as the electron acceptor or they are plain carbon electrodes in a ferricyanide solution. The characteristics and performance of these two cathodes were compared using a two-chambered MFC. Power generation using the Pt-carbon cathode and dissolved oxygen (saturated) reached a maximum of 0.097 mW within 120 h after inoculation (wastewater sludge and 20 mM acetate) when the cathode was equal size to the anode (2.5 x 4.5 cm). Once stable power was generated after replacing the MFC with fresh medium (no sludge), the Coulombic efficiency ranged from 63 to 78%. Power was proportional to the dissolved oxygen concentration in a manner consistent with Monod-type kinetics, with a half saturation constant of K(DO) = 1.74 mg of O2/L. Power increased by 24% when the cathode surface areas were increased from 22.5 to 67.5 cm2 and decreased by 56% when the cathode surface area was reduced to 5.8 cm2. Power was also substantially reduced (by 78% to 0.02 mW) if Pt was not used on the cathode. By using ferricyanide instead of dissolved oxygen, the maximum power increased by 50-80% versus that obtained with dissolved oxygen. This result was primarily due to increased mass transfer efficiencies and the larger cathode potential (332 mV) of ferricyanide than that obtained with dissolved oxygen (268 mV). A cathode potential of 804 mV (NHE basis) is theoretically possible using dissolved oxygen, indicating that further improvements in cathode performance with oxygen as the electron acceptor are possible that could lead to increased power densities in this type of MFC.     

Lignin-containing Microfibrillated Cellulose Prepared from Corncob Residue via Calcium Hydroxide Co-grinding and Its Application in Paper Reinforcement

In this study, lignin-containing microfibrillated cellulose (MFC) was prepared from corncob residue after xylose extraction via co-grinding with calcium hydroxide. The product was then compared with the MFC obtained by direct grinding and applied to strengthen paper. The chemical composition and morphological structure analysis results showed that the corncob residue can be used to prepare lignin-containing MFC and does not require further purification. Moreover, the co-grinding with calcium hydroxide is easier to fibrillate corncob residue. The MFC obtained by co-grinding with calcium hydroxide had a higher aspect ratio, and its surface was coated with calcium carbonate nanoparticles. MFCs obtained by both the methods mentioned above had an obvious strengthening effect on paper. Compared with the paper without MFC, the tensile index, elongation, burst index, and folding strength of the paper with MFC obtained by co-grinding with calcium hydroxide significantly increased by 17.5%, 22.1%, 19.5%, and 157.1%, respectively. This study provides a novel idea for the utilization of corncob residue, which may enhance the value and promote the comprehensive utilization of corn by-products.     

Microbial fuel cell operation with continuous biological ferrous iron oxidation of the catholyte

The oxygen reduction rate at the cathode is a limiting factor in microbial fuel cell (MFC) performance. In our previous study, we showed the performance of an MFC with ferric iron (Fe3+) reduction at the cathode. Instead of oxygen, ferric iron was reduced to ferrous iron (Fe2+) at the cathode with a bipolar membrane between the anode and cathode compartment. This resulted in a higher cathode potential than is usually obtained with oxygen on metal-based chemical catalysts in MFCs. In this study, we investigated the operation of the same MFC with ferric iron reduction at the cathode and simultaneous biological ferrous iron oxidation of the catholyte. We show that the immobilized microorganism Acidithiobacillus ferrooxidans is capable of oxidizing ferrous iron to ferric iron at a rate high enough to ensure an MFC power output of 1.2 W/m2 and a current of 4.4 A/m2. This power output was 38% higher than in our previous study at a similar current density without ferrous iron oxidation. The bipolar membrane is shown to split water into 65-76% of the needed protons and hydroxides. The other part of the protons was supplied as H2SO4 to the cathode compartment. The remaining charge was transported by K+ and HSO4-/SO4(2-) from the one compartment to the other. This resulted in increased salt concentrations in the cathode. The increased salt concentrations reduced the ohmic losses and enabled the improved MFC power output. Iron could be reversibly removed from the bipolar membrane by exchange with protons.     

Environmental risk assessment of paroxetine

Paroxetine hydrochloride hemihydrate (the active ingredient in Paxil) is a pharmaceutical compound used for the treatment of depression, social anxiety disorder, obsessive compulsive disorder, panic disorder, and generalized anxiety disorder. Paroxetine (PA) is extensively metabolized in humans, with about 97% of the parent compound being excreted as metabolites through the urine and feces of patients. Therefore PA and metabolites have the potential to be discharged into wastewater treatment systems after therapeutic use. PA and its major human metabolite (PM) were investigated using studies designed to describe physical/chemical characteristics and determine their fate and effects in the aquatic environment. A significant portion of the PM entering a wastewater treatment plant would be expected to biodegrade given the higher activated sludge solids concentrations present in a typical wastewater treatment plant. The potential for direct photolysis of PM is also possible based on photolysis results for PA itself. These results provide strong support for expecting that PA and PM residuals will not persist in the aquatic environment after discharge from a wastewater treatment facility. This conclusion is also supported by the results of a USGS monitoring study, where no PM was detected in any of the samples at the 260 ng/L reporting limit. The results presented here also demonstrate the importance of understanding the human metabolism of a pharmaceutical so that the appropriate molecule(s) is used for fate and effects studies. In addition to the PA fate studies, PM was investigated using studies designed to determine potential environmental effects and a predicted no effect level (PNEC). The average measured activated sludge respiration inhibition value (EC50) for PM was 82 mg/L. The measured Microtox EC50 value was 33.0 mg/L, while the Daphnia magna EC50 value was 35.0 mg/L. The PNEC for PM was calculated to be 35.0 microg/L. Fate data were then used in a new watershed-based environmental risk assessment model, PhATE, to predict environmental concentrations (PECs). Comparison of the calculated PECs with the PNEC allows an assessment of potential environmental risk. Within the 1-99% of stream segments in the PhATE model, PEC values ranged from 0.003 to 100 ng/L. The risk assessment PEC/PNEC ratios ranged from approximately 3 x 10(-8) to approximately 3 x 10(-3), indicating a wide margin of safety, since a PEC/PNEC ratio <1 is generally considered to represent a low risk to the environment. In addition, Microtox studies carried out on PM biodegradation byproducts indicated no detectable residual toxicity. Any compounds in the environment as a result of the biodegradation of PM should be innocuous polar byproducts that should not exert any toxic effects.     

Pesticide uptake in potatoes: model and field experiments

A dynamic model for uptake of pesticides in potatoes is presented and evaluated with measurements performed within a field trial in the region of Boyaca?, Colombia. The model takes into account the time between pesticide applications and harvest, the time between harvest and consumption, the amount of spray deposition on soil surface, mobility and degradation of pesticide in soil, diffusive uptake and persistence due to crop growth and metabolism in plant material, and loss due to food processing. Food processing steps included were cleaning, washing, storing, and cooking. Pesticide concentrations were measured periodically in soil and potato samples from the beginning of tuber formation until harvest. The model was able to predict the magnitude and temporal profile of the experimentally derived pesticide concentrations well, with all measurements falling within the 90% confidence interval. The fraction of chlorpyrifos applied on the field during plant cultivation that eventually is ingested by the consumer is on average 10(-4)-10(-7), depending on the time between pesticide application and ingestion and the processing step considered.     

Electricity generation by Rhodopseudomonas palustris DX-1

Bacteria able to generate electricity in microbial fuel cells (MFCs) are of great interest, but there are few strains capable of high power production in these systems. Here we report that the phototrophic purple nonsulfur bacterium Rhodopseudomonas palustris DX-1, isolated from an MFC, produced electricity at higher power densities (2720 +/- 60 mW/m2) than mixed cultures in the same device. While Rhodopseudomonas species are known for their ability to generate hydrogen, they have not previously been shown to generate power in an MFC, and current was generated without the need for light or hydrogen production. Strain DX-1 utilizes a wide variety of substrates (volatile acids, yeast extract, and thiosulfate) for power production in different metabolic modes, making it highly useful for studying power generation in MFCs and generating power from a range of simple and complex sources of organic matter. These results demonstrate that a phototrophic purple nonsulfur bacterium can efficiently generate electricity by direct electron transfer in MFCs, providing another model microorganism for MFC investigations.