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Risk assessment of boron in glass wool insulation 全文
2009
Jensen, Allan Astrup
Background, aim and scope Glass wools are man-made vitreous fibres, which consist principally of sodium, calcium and magnesium silicates, but may contain smaller amounts of other elements, including boron. The boron contents originate from the use of borates in the glass melting process as a glass former and a flux agent. During the production and application of glass wool insulation products, workers may legally be exposed to glass fibre up to the occupational limit value, commonly of 1 fibre/cm³. However, in practice, the fibre exposure will be at least ten times lower. Boron is a non-metallic element widely distributed in nature, where it occurs as boric acid, borates and borosilicates. Humans are mainly exposed to boron via vegetarian food and drinking water, mineral supplements and various consumer products. Boron is an essential element for plant growth, but the essentiality for humans is not proven, although intakes of trace amounts of the element seem to be useful for bone health and proper brain function; higher concentrations of boron, however, may be toxic. In relation to the European Union legislation on dangerous substances, an EU Expert Group has recommended classifying boric acid and borates with risk phrases for reproductive toxicity. The aim of this paper is to assess whether the new EU hazard classification of boron compounds should imply that glass wool products used for building insulation in the future should be labelled, “may impair fertility and cause harm to the unborn child”, because of the low boron content. Materials and methods Boron intakes are estimated in a worst-case occupational situation with human exposure to glass wool fibres at the occupational limit of 1 fibre/cm³ by calculation of the mass of the amount of fibres inhaled during an 8-h work day. Fibres are supposed to be cylinders of glass with a length of 30 μm, an average diameter of 1.5-2 μm and containing either 1.5% or 3.5% boron. As a worst-case scenario, the density of the fibres is set to 2,700 kg/m³. The inhalation rate of the individuals at moderate work load was set to 2 m³/h. A worst-case scenario also corresponds to 100% retention and to 100% solubility of the retained fibres in the lungs. Results With the normal boron content of 1.5% in glass wool fibres for building insulation, the extra daily occupational boron intake/uptake will be 0.03-0.06 mg B for 5 days a week. For more uncommon glass wool with maximum boron content of 3.5%, the worst-case daily boron intake/uptake will be 0.08-0.16 mg B. The main boron exposure in the general population is from vegetarian food, and the average daily dietary intake with food is estimated to 1.2-1.5 mg B/day. In addition, significant intakes may come with drinking water, especially from mineral water. In some instances, exposure from mineral supplements, cosmetics and other consumer products may be significant. For example, individuals taking mineral supplements, e.g. for bodybuilding, may have an additional intake to that of 1-10 mg/day. During the years, various organisations have recommended safe intake values for boron. Recently, the Scientific Panel on Dietetic Products, Nutrition and Allergies of the European Food Safety Authority (EFSA) has established the 'Tolerable Upper Intake Level' (UL) for the intake of boron (boric acid and borates) at 0.16 mg B/kg body weight per day or about 10 mg B/day for an adult. Discussion The calculated, worst-case exposure scenario during an 8-h work day will result in an extra daily boron intake that only corresponds to about 10% of the average daily adult boron intakes through food and drinks of about 1.5 mg. The inter-individual variations in boron intakes from foods, water and supplements will be much greater than an eventual, very worst-case, additional intake of boron from inhalation of glass wool fibres. In addition, the combined intakes are far lower than the 'Tolerable Upper Intake Level' of 10 mg B/day for a person weighing 60 kg, as recommended by the European Food Safety Agency. The potential boron intake from inhalation of glass wool fibres is also much lower than boron intakes by workers in the boron industry, who at the present occupational limit value will be exposed to 50 mg of boron 5 days a week, or 100 times more than the worst case for glass wool fibres. Furthermore, in practice, exposure levels will mostly be ten to 100 times lower than the occupational limit used here as a worst case. Conclusions The estimated boron intake from inhalation of glass wool fibres in occupational settings will be insignificant and without any health risks, even in the case of non-compliance with the occupational limit value. Any proposal requiring hazard labels on commercial glass wool products for building insulation, because of the boron content, is not supported by the present scientific knowledge. Recommendations and perspectives The European Commission should ensure that the new EU hazard classification of boron compounds is not applied to commercial glass wool products for building insulation having a low content of boron.
显示更多 [+] 显示较少 [-]Contents and sources of DDT impurities in dicofol formulations in Turkey 全文
2009
Turgut, Cafer | Gokbulut, Cengiz | Cutright, Teresa J
Background, aim, and scope Dicofol is widely used as a pesticide in agriculture applications. Since dicofol is mainly synthesized from dichlorodiphenyltrichlorethane (DDT), it contains DDT as an impurity. The European Community has forced Prohibition Directive 79/117/EEC to reduce DDT in dicofol formulations. Specifically, DDT content in a dicofol formulation cannot exceed 0.1%. The goal of this project was to determine the DDT content in dicofol formulations used in Turkey. Materials and methods Samples of all the dicofol formulations in Turkey were collected to quantify DDT and DDT-related compounds. Four replicates were used for each sample. GC/MS/MS was used to analyze p,p' and o,p' isomers of DDT, DDD, and DDE. A HPLC was used to determine p,p'-Cl-DDT concentrations. Results The total DDT content of the formulated dicofol was found between 0.3% and 14.3%. The concentration of p,p'-DDE ranged from 167 to 1,042 mg kg⁻¹ in dicofol samples. p,p'-DDT concentrations were found to be 32 to 183 mg kg⁻¹. The o,p'-DDT level ranged from 2 to 34 mg kg⁻¹ in the dicofol formulations analyzed. Discussion It was estimated that 617.8 kg of DDT was released from dicofol. The main impurity was identified as p,p-Cl-DDT. Based on these results, dicofol serves as a continuing source of DDT contamination. Conclusions All DDT concentrations in dicofol samples analyzed were higher than the permitted 0.1% level of Prohibition Directive 79/117/EEC. The reduction of dicofol is critical since it serves as a continual source of DDT contamination. Recommendations and perspectives DDT has been found in soil, water, and air samples. Dicofol has been identified as a contributor to continued DDT contamination in soil and water. More studies are needed to ascertain the source of DDT in the air.
显示更多 [+] 显示较少 [-]Climate and land-use changes affecting river sediment and brown trout in alpine countries--a review 全文
2009
Scheurer, Karin | Alewell, Christine | Bänninger, Dominik | Burkhardt-Holm, Patricia
Background, aim, and scope Catch decline of freshwater fish has been recorded in several countries. Among the possible causes, habitat change is discussed. This article focuses on potentially increased levels of fine sediments going to rivers and their effects on gravel-spawning brown trout. Indications of increased erosion rates are evident from land-use change in agriculture, changes in forest management practices, and from climate change. The latter induces an increase in air and river water temperatures, reduction in permafrost, changes in snow dynamics and an increase in heavy rain events. As a result, an increase in river sediment is likely. Suspended sediment may affect fish health and behaviour directly. Furthermore, sediment loads may clog gravel beds impeding fish such as brown trout from spawning and reducing recruitment rates. To assess the potential impact on fine sediments, knowledge of brown trout reproductive needs and the effects of sediment on brown trout health were evaluated. Approach We critically reviewed the literature and included results from ongoing studies to answer the following questions, focusing on recent decades and rivers in alpine countries. Have climate change and land-use change increased erosion and sediment loads in rivers? Do we have indications of an increase in riverbed clogging? Are there indications of direct or indirect effects on brown trout from increased suspended sediment concentrations in rivers or from an increase in riverbed clogging? Results Rising air temperatures have led to more intensive precipitation in winter months, earlier snow melt in spring, and rising snow lines and hence to increased erosion. Intensification of land use has supported erosion in lowland and pre-alpine areas in the second half of the twentieth century. In the Alps, however, reforestation of abandoned land at high altitudes might reduce the erosion risk while intensification on the lower, more easily accessible slopes increases erosion risk. Data from laboratory experiments show that suspended sediments affect the health and behaviour of fish when available in high amounts. Point measurements in large rivers indicate no common lethal threat and suspended sediment is rarely measured continuously in small rivers. However, effects on fish can be expected under environmentally relevant conditions. River bed clogging impairs the reproductive performance of gravel-spawning fish. Discussion Overall, higher erosion and increased levels of fine sediment going into rivers are expected in future. Additionally, sediment loads in rivers are suspected to have considerably impaired gravel bed structure and brown trout spawning is impeded. Timing of discharge is put forward and is now more likely to affect brown trout spawning than in previous decades. Conclusions Reports on riverbed clogging from changes in erosion and fine sediment deposition patterns, caused by climate change and land-use change are rare. This review identifies both a risk of increases in climate erosive forces and fine sediment loads in rivers of alpine countries. Increased river discharge and sediment loads in winter and early spring could be especially harmful for brown trout reproduction and development of young life stages. Recently published studies indicate a decline in trout reproduction from riverbed clogging in many rivers in lowlands and alpine regions. However, the multitude of factors in natural complex ecosystems makes it difficult to address a single causative factor. Recommendations and perspectives Further investigations into the consequences of climate change and land-use change on river systems are needed. Small rivers, of high importance for the recruitment of gravel-spawning fish, are often neglected. Studies on river bed clogging are rare and the few existing studies are not comparable. Thus, there is a strong need for the development of methods to assess sediment input and river bed clogging. As well, studies on the effects to fish from suspended sediments and consequences of gravel beds clogging under natural conditions are urgently needed.
显示更多 [+] 显示较少 [-]Effects of triclosan on zebrafish early-life stages and adults 全文
2009
Oliveira, Rhaul | Domingues, Inês | Grisolia, Cesar Koppe | Soares, Amadeu M. V. M.
Background, aim and scope The biocide triclosan (TCS) is commonly used in personal care, acrylic, plastic, and textiles products. TCS has been detected in surface water in several countries, and its ecological impact is largely unknown. In this work, the toxicity of TCS in zebrafish (Danio rerio), embryos and adults was studied. Several lethal and sub-lethal endpoints were analysed in organisms exposed to TCS such as mortality, embryo development and behaviour, hatching, micronuclei and biochemical markers (cholinesterase (ChE), glutathione S-transferase (GST) and lactate dehydrogenase (LDH)). Materials and methods Embryo/larvae assay followed the OECD guideline on Fish Embryo Toxicity Test. Embryos were exposed at nominal concentrations of 0.1, 0.3, 0.5, 0.7 and 0.9 mg/l of TCS for 6 days and were inspected daily with the help of a stereomicroscopy for mortality, developmental parameters (otolith formation, eye and body pigmentation, somite formation, heart beat, tail circulation, detachment of the tail-bud from the yolk sac) and hatching. A similar test was run to obtain larvae for ChE, GST and LDH analysis. The adult test followed the OECD Guideline TG 203 in semi-static conditions. Adult zebrafish of similar length and age were exposed to nominal concentrations of 0.1, 0.2, 0.3, 0.4 and 0.5 mg/l of TCS for 96 h and were inspected daily for mortality and behaviour alterations. A second test was run to obtain organs for biomarkers analysis: Heads, muscles and gills were isolated and snap-frozen in eppendorfs and used for ChE, LDH and GST determinations, respectively. Adult zebrafish testing also comprised a third test for micronucleus analysis in which the nominal concentrations of 0, 0.175 and 0.350 mg/l were used. Peripheral blood was obtained by cardiac puncture and used for the analysis. Results TCS showed acute toxicity for embryo/larvae (96 h LC₅₀ = 0.42 mg/l) and delayed hatching. Moreover, embryo toxicity was evident: Delay on the otolith formation and eye and body pigmentation were found, and malformations were also evident, including spine malformations, pericardial oedema and undersize. Biomarkers levels were affected: ChE and LDH activity were increased in larvae exposed to 0.25 mg/l, and GST activity was increased in larvae exposed to 0.25 and 0.35 mg/l. TCS also demonstrated acute toxicity to adult zebrafish (96 h LC₅₀ = 0.34 mg/l). However, TCS did not change biomarkers levels and did not elicit a micronucleus in adults. Discussions Despite the fact that similar 96 h LC₅₀ values have been found for D. rerio embryos and adults (0.42 and 0.34 mg/l, respectively), the embryo assay was much more informative, showing important effects at several levels, including teratogenic response, hatching delay and alteration of biomarker levels. TCS does not seem to be genotoxic for adult fish or to interfere with biomarkers levels at the concentrations tested. Conclusions TCS has deleterious effects on zebrafish adults and during early stages, (including embryotoxicity, hatching delay and alterations of biomarkers levels). The range of endpoints used on the embryo test allows an integrated analysis that contributes to a better understanding of the toxicity and mode of action of TCS. Recommendations and perspectives Future works should focus on a deeper investigation of TCS modes of action on zebrafish early-life stages. As embryo testing was revealed to be so informative, a refinement of the test could be made, including other endpoints such as different biochemical markers as well as DNA microarrays to assess a gene expression level for the effect of exposure to TCS. In the perspective of risk assessment, these endpoints should be explored in order to assess their usefulness as early warning signs and links should be sought between these short-term tests and effects of long-term exposures as it is observed in more realistic scenarios.
显示更多 [+] 显示较少 [-]Reduction of nitrogen loss and Cu and Zn mobility during sludge composting with bamboo charcoal amendment 全文
2009
Hua, Li | Wu, Weixiang | Liu, Yuxue | McBride, Murray B. | Chen, Yingxu
Background, aim, and scope Composting is an effective treatment process to realize sludge land application. However, nitrogen loss could result in the reduction of nutrient value of the compost products and the stabilization effect of composting on heavy metal concentration and mobility in sludge has been shown to be very limited. Materials and methods Laboratory-scale experiments were carried out to investigate the effects of bamboo charcoal (BC) on nitrogen conservation and mobility of Cu and Zn during sludge composting. Results The result indicated that the incorporation of BC into the sludge composting material could significantly reduce nitrogen loss. With 9% BC amendment, total nitrogen loss at the end of composting decreased 64.1% compared with no BC amendment (control treatment). Mobility of Cu and Zn in the sludge may also have been lessened, based on the decline in diethylenetriaminepentaacetic acid-extractable Cu and Zn contents of composted sludge by 44.4% and 19.3%, respectively, compared to metal extractability in the original material. Discussion Ammonia adsorption capability of BC might be the main reason for the retention of nitrogen in sludge composting materials. Decrease of extractable Cu²⁺ and Zn²⁺ in the composting material mainly resulted from the adsorption of both metals by BC. Conclusions Incorporation of BC into composting material could significantly lessen the total nitrogen loss during sludge composting. Mobility of heavy metals in the sludge composting material could also be reduced by the addition of BC. Recommendations and perspectives Bamboo charcoal could be an effective amendment for nitrogen conservation and heavy metal stabilization in sludge composts. Further research into the effect of BC-amended sludge compost material on soil properties, bioavailability of heavy metals, and nutrient turnover in soil needs to be carried out prior to the application of BC-sludge compost in agriculture.
显示更多 [+] 显示较少 [-]Black layers on historical architecture 全文
2009
Toniolo, Lucia | Zerbi, Carlotta M. | Bugini, Roberto
Background, aim and scope The external surface of any building in urban polluted environment is unavoidably destined to be covered with layers that assume a grey to black colour and are generally called 'black crusts'. These, according to standard protocols and glossary, are deteriorated surface layers of stone material; they can have variable thickness, are hard and fragile and can detach spontaneously from the substrate, which, in general, is quite decayed. Plain visual examination may lead to consider 'black crusts' all similar, whilst only a careful diagnostic investigation can distinguish 'black crusts' and the consequences of their formation on stone substrates. In this paper, various black layers on marble are studied and compared and the morphological and compositional characteristics discussed according to the related mechanisms of formation. Differences between old (hundred years) and recent crusts (30 years) are investigated and pointed out. Materials and methods Samples of black crusts collected from the Milan Cathedral façade (Candoglia Marble) have been studied and compared with the careful and synergic employ of traditional techniques: optical (transmission and reflected VIS light) and electron microscopy, X-ray spectrometry and micro-Fourier transform infrared spectroscopy. Results Visual examination of loose fragments does not allow to point out outstanding differences amongst the various samples; black layers have similar main mineral components, gypsum and airborne particles, with different spatial distribution. The microscopic studies allowed to point out the porosity differences, the gypsum crystallisation habit, different amount of embedded particles, level and progress of marble decay. Discussion The observations lead to define three main types of black crusts: black crust deriving from marble sulphation, compact deposit and encrustation due to exogenic materials deposition. Black crusts show evidence of sulphation in progress, without a clear continuity solution between crust and marble; the lack of separation is particularly evident in 'recent' crust, where the sulphation process is more active. Black compact deposits show a higher porosity than black crusts because gypsum is not coming from the chemical corrosion of the substrate but from outside; actually, in the former case, the substrate is sound. Encrustations show a highly regular crystal organisation of gypsum (close packed tabular crystals) that cannot be traced back to casual atmospheric deposit or to corrosion of the substrate but rather to the crystallisation of a solution coming from an external source. Also in this case, the marble is sound; evidence of the effect of some protection treatment is pointed out. Conclusions In spite of the apparent similarity of the examined samples, analytical results have evidenced three main types of black crusts: black crust with decayed substrate, compact deposit and black encrustation showing a sound substrate underneath. Experimental evidence of calcite grains sulphation in progress, taking place according to a model recently proposed, has been observed. Sulphation process is prevented where particular conservation treatments had been applied in the past. Recommendations and perspectives New experimental studies can be focussed to understand the specific conditions (measurements of micro-climatic and thermodynamic parameters) and mechanisms for black crusts formation in situ. The problem of the kinetic of the sulphation process of marble, the assessment of black layers formation in the case of different carbonate stone materials and the study of acid attack in presence of surface protecting layers deserve further investigation.
显示更多 [+] 显示较少 [-]The Rhine red, the fish dead--the 1986 Schweizerhalle disaster, a retrospect and long-term impact assessment 全文
2009
Giger, W (Walter)
Background The November 1, 1986 fire at a Sandoz Ltd. storehouse at Schweizerhalle, an industrial area near Basel, Switzerland, resulted in chemical contamination of the environment. The storehouse, which was completely destroyed by the fire, contained pesticides, solvents, dyes, and various raw and intermediate materials. The majority of the approximately 1,250 t of stored chemicals was destroyed in the fire, but large quantities were introduced into the atmosphere, into the Rhine River through runoff of the fire-fighting water, and into the soil and groundwater at the site. The chemicals discharged into the Rhine caused massive kills of benthic organisms and fish, particularly eels and salmonids. Public and private reaction to the fire and subsequent chemical spill was very strong. This happened only a few months after the Chernobyl accident and it destroyed the myth of immunity of Switzerland regarding such catastrophes. Aim This article reviews the damaging events of November 1986 and aims at striking stock two decades later. Results and discussion In the aftermath of this once-per-century accident, the aim was to obtain new knowledge for the environmental sciences and to achieve progress for water pollution control issues. The following themes are discussed: mitigation measures by the chemical industry and by the governmental authorities, activities of environmental protection organizations, chemical and biological monitoring, alert organization, ecological damages, ecotoxicological effects assessment, recovery and alteration of the river biology, return of the salmon, drinking water supplies, research programs, education of environmental scientists, and visions for the future. Conclusions The catastrophic pollution of the Rhine in November 1986 has triggered by the openly visible damages of the river biology that subsequently significant progress was made towards the prevention of such environmental catastrophes. The crucial risk reduction measures in the chemical industry, legal regulations and controls as well as chemical and biological monitoring of the river water quality were substantially improved. Politics and chemical industry have learned their lectures and have proceeded accordingly. Recommendations A drastic acute contamination, as it has happened at Schweizerhalle in 1986, is clearly recognizable by the toxic effects, which it is causing. This can lead to mitigation activities, which are positive considering a long-term perspective. However, the less obvious effects of chronic water pollution should receive more attention as well as the ongoing alteration of the biocenosis. A high water quality must be demanded for using water from the Rhine to produce drinking water. In that context, micropollutants should also be considered and particular attention should be payed to emerging contaminants. Perspectives The big chemical storehouse fire of 1986 had an important impact on the transboundary cooperation and has improved the willingness for international cooperation. The fire catastrophe of Schweizerhalle has triggered many activities in particular for the Rhine River. Overall, the effects are positive on the basis of a long-term perspective. The applied whole basin approach gives an example on a global basis for other river systems, which still are more heavily polluted.
显示更多 [+] 显示较少 [-]Environmental and socioeconomic assessment of impacts by mining activities--a case study in the Certej River catchment, Western Carpathians, Romania 全文
2009
Zobrist, Jürg | Sima, Mihaela | Dogaru, Diana | Senila, Marin | Yang, Hong | Popescu, Claudia | Roman, Cecilia | Bela, Abraham | Frei, Linda | Dold, Bernhard | Bălteanu, Dan
Background, aim and scope In the region of the Apuseni Mountains, part of the Western Carpathians in Romania, metal mining activities have a long-standing tradition. These mining industries created a clearly beneficial economic development in the region. But their activities also caused impairments to the environment, such as acid mine drainage (AMD) resulting in long-lasting heavy metal pollution of waters and sediments. The study, established in the context of the ESTROM programme, investigated the impact of metal mining activities both from environmental and socioeconomic perspectives and tried to incorporate the results of the two approaches into an integrated proposition for mitigation of mining-related issues. Study site The small Certej catchment, situated in the Southern Apuseni Mountains, covers an area of 78 km². About 4,500 inhabitants are living in the basin, in which metal mining was the main economic sector. An open pit and several abandoned underground mines are producing heavy metal-loaded acidic water that is discharged untreated into the main river. The solid wastes of mineral processing plants were deposited in several dumps and tailings impoundment embodying the acidic water-producing mineral pyrite. Methods The natural science team collected samples from surface waters, drinking water from dug wells and from groundwater. Filtered and total heavy metals, both after enrichment, and major cations were analysed by inductively coupled plasma optical emission spectroscopy (ICP-OES). Major anions in waters, measured by ion chromatography, alkalinity and acidity were determined by titration. Solid samples were taken from river sediments and from the largest tailings dam. The latter were characterised by X-ray fluorescence and X-ray diffraction. Heavy metals in sediments were analysed after digestion. Simultaneously, the socioeconomic team performed a household survey to evaluate the perception of people related to the river and drinking water pollution by way of a logistic regression analysis. Results and discussion The inputs of acid mine waters drastically increased filtered heavy metal concentrations in the Certej River, e.g. Zn up to 130 mg L⁻¹, Fe 100 mg L⁻¹, Cu 2.9 mg L⁻¹, Cd 1.4 mgL⁻¹ as well as those of SO₄ up to 2.2 g L⁻¹. In addition, river water became acidic with pH values of pH 3. Concentrations of pollutant decreased slightly downstream due to dilution by waters from tributaries. Metal concentrations measured at headwater stations reflect background values. They fell in the range of the environmental quality standards proposed in the EU Water Framework Directive for dissolved heavy metals. The outflow of the large tailing impoundment and the groundwater downstream from two tailings dams exhibited the first sign of AMD, but they still had alkalinity. Most dug wells analysed delivered a drinking water that exhibited no sign of AMD pollution, although these wells were a distance of 7 to 25 m from the contaminated river. It seems that the Certej River does not infiltrate significantly into the groundwater. Pyrite was identified as the main sulphide mineral in the tailings dam that produces acidity and with calcite representing the AMD-neutralising mineral. The acid-base accounting proved that the potential acid-neutralising capacity in the solid phases would not be sufficient to prevent the production of acidic water in the future. Therefore, the open pits and mine waste deposits have to be seen as the sources for AMD at the present time, with a high long-term potential to produce even more AMD in the future. The socioeconomic study showed that mining provided the major source of income. Over 45% of the households were partly or completely reliant on financial compensations as a result of mine closure. Unemployment was considered by the majority of the interviewed persons as the main cause of social problems in the area. The estimation of the explanatory factors by the logistic regression analysis revealed that education, household income, pollution conditions during the last years and familiarity with environmental problems were the main predictors influencing peoples' opinion concerning whether the main river is strongly polluted. This model enabled one to predict correctly 77% of the observations reported. For the drinking water quality model, three predictors were relevant and they explained 66% of the observations. Conclusions Coupling the findings from the natural science and socioeconomic approaches, we may conclude that the impact of mining on the Certej River water is high, while drinking water in wells is not significantly affected. The perceptions of the respondents to pollution were to a large extent consistent with the measured results. Recommendations and perspectives The results of the study can be used by various stakeholders, mainly the mining company and local municipalities, in order to integrate them in their post-mining measures, thereby making them aware of the potential long-term impact of mining on the environment and on human health as well as on the local economy.
显示更多 [+] 显示较少 [-]Preparation of calcium oxalate--bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters 全文
2009
Wang, Hong-Yan | Gao, Hong-Wen
Background, aim, and scope Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable. Materials and methods On the basis of the chemical coprecipitation of calcium oxalate (CaC₂O₄), bromopyrogallol red (BPR) was embedded during the growing of CaC₂O₄ particles. The ternary C₂O₄ ²⁻-BPR-Ca²⁺ sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV. Results The saturation number of BPR binding to CaC₂O₄ reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 x 10⁵ M⁻¹. Over 80% of the sorbent particles are between 0.7 and 1.02 μm, formed by the aggregation of the global CaC₂O₄/BPR inclusion grains of 30-50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC₂O₄/BPR inclusion material adsorbed EV over two times more efficiently than the activated carbon. The adsorption of EV on the CaC₂O₄/BPR inclusion sorbent was complete in only 5 min and the sedimentation complete in 1 h. However, those of EV onto activated carbon took more than 1.5 and 5 h, respectively. The treatment of methylene blue and malachite green dye wastewaters indicated that only 0.4% of the sorbent adsorbed over 80% of color substances. Besides, the material can also adsorb heavy metals by complexation with BPR. Over 90% of Pb²⁺, and approximately 50% of Cd²⁺ and Cu²⁺, were removed in a high Zn²⁺-electroplating wastewater when 3% of the material was added. Eighty-six percent of Cu²⁺, and 60% of Ni²⁺ and Cd²⁺, were removed in a high Cd²⁺-electroplating wastewater. Discussion The embedment of BPR into CaC₂O₄ particles responded to the Langmuir isothermal adsorption. As the affinity ligand of Ca²⁺, BPR with sulfonic groups may be adsorbed into the temporary electric double layer during the growing of CaC₂O₄ particles. Immediately, C₂O₄ ²⁻ captured the Ca²⁺ to form the CaC₂O₄ outer enclosed sphere. Thus, BPR may be released and embedded as a sandwich between CaC₂O₄ layers. The adsorption of EV on the sorbent obeyed the Langmuir isothermal equation and adsorption is mainly due to the ion-pair attraction between EV and BPR. Different from the inclusion sorbent, the activated carbon depended on the specific surface area to adsorb organic substances. Therefore, the adsorption capacity, equilibrium, and sedimentation time of the sorbent are much better than activated carbon. The interaction of heavy metals with the inclusion sorbent responded to their coordination. Conclusions By characterizing the C₂O₄ ²⁻-BPR-Ca²⁺ inclusion material using various modern instruments, the ternary in situ embedment particle, [(CaC₂O₄)₉₅(BPR)] n ²n⁻, an electronegative, micron-sized adsorbent was synthesized. It is selective, rapid, and highly effective for adsorbing cationic dyes and heavy metals. Moreover, the adsorption is hardly subject to the impact of electrolytes. Recommendations and perspectives The present work provides a simple and valuable method for preparing the highly effective adsorbent. If a concentrated BPR wastewater was reused as the inclusion reactant, the sorbent will be low cost. By selecting the inclusion ligand with a special structure, we may prepare some particular functional materials to recover the valuable substances from seriously polluted wastewaters. The recommended method will play a significant role in development of advanced adsorption materials.
显示更多 [+] 显示较少 [-]What determines selection and abandonment of a foraging patch by wild giant pandas (Ailuropoda melanoleuca) in winter? 全文
2009
Zhang, Zejun | Zhan, Xiangjiang | Yan, Li | Li, Ming | Hu, Jinchu | Wei, Fuwen
Background, aim, and scope Foraging patches can be described as a nested hierarchy of aggregated resources, implying that study of foraging by wild animals should be directed across different spatial scales. However, almost all previous research on habitat selection by the giant panda has concentrated upon one scale. In this research, we carried out a field study to understand foraging patch selection by giant pandas in winter at both microhabitat and feeding site scales and, for the first time, attempted to understand how long it would stay at the feeding sites before moving on. Materials and methods The field survey was conducted from November 2002 to March 2003 at Fengtongzhai Nature Reserve (102°48'-103°00' E, 30°19'-30°47' N), Baoxing County of Sichuan Province, China, to collect data in both microhabitat and control plots. The microhabitat plots were located by fresh feces or foraging traces left by giant pandas, and the control plots were established to reflect the environment. Within each microhabitat plot, one 1 x 1 m² plot was centralized at the center of each feeding site, in which numbers of old bamboos and old shoots, including eaten and uneaten, were counted, respectively. Results The results showed that winter microhabitats selected by this species were characteristic of gentle slopes and high old-shoot proportions and that the latter was even higher at feeding sites. Two selection processes, namely, from the environment to microhabitats and from the latter to feeding sites, were found during this species' foraging patch utilization. Giant pandas preferred to eat old shoots to old bamboo at feeding sites in winter and did not leave unless old-shoot density fell to lower than the average in the environment. Discussion Both microhabitats and feeding sites selected by giant pandas were characteristic of high old-shoot density, indicating that the preferred food item had a significant influence upon its foraging patch selection. The preference for gentle slopes by giant pandas was presumed to save energy in movement or reflect the need to sit and free its fore-limbs to grasp bamboo culms when feeding but also seemed to be correlated with an easier access to old shoots. The utilization of old shoots at feeding sites was assumed to help maximize energy or nutrient intake during their foraging. Conclusions The difference between microhabitat plots and control plots and between microhabitats and feeding sites uncovered a continuous selection process from the environment via microhabitats to feeding sites. The utilization of old shoots at feeding sites was parallel to the marginal value theorem. The selection and abandonment of foraging patches by giant pandas was an optimal behavioral strategy adapted to their peculiar food with high cellulose and low protein. Recommendations and perspectives Our results uncovered the importance of multiple scales in habitat selection research. To further understand the process of habitat selection, future research should pay more attention to resolve the question of how to locate foraging patches under dense bamboo forests by the giant panda, which was traditionally considered to have poor eyesight, although our research has answered what type of habitats the giant panda prefers and when to leave.
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