Screening tests for hazard classification of complex waste materials – Selection of methods

In this study we describe the development of an alternative methodology for hazard characterization of waste materials. Such an alternative methodology for hazard assessment of complex waste materials is urgently needed, because the lack of a validated instrument leads to arbitrary hazard classification of such complex waste materials. False classification can lead to human and environmental health risks and also has important financial consequences for the waste owner. The Hazardous Waste Directive (HWD) describes the methodology for hazard classification of waste materials. For mirror entries the HWD classification is based upon the hazardous properties (H1–15) of the waste which can be assessed from the hazardous properties of individual identified waste compounds or – if not all compounds are identified – from test results of hazard assessment tests performed on the waste material itself. For the latter the HWD recommends toxicity tests that were initially designed for risk assessment of chemicals in consumer products (pharmaceuticals, cosmetics, biocides, food, etc.). These tests (often using mammals) are not designed nor suitable for the hazard characterization of waste materials. With the present study we want to contribute to the development of an alternative and transparent test strategy for hazard assessment of complex wastes that is in line with the HWD principles for waste classification. It is necessary to cope with this important shortcoming in hazardous waste classification and to demonstrate that alternative methods are available that can be used for hazard assessment of waste materials. Next, by describing the pros and cons of the available methods, and by identifying the needs for additional or further development of test methods, we hope to stimulate research efforts and development in this direction. In this paper we describe promising techniques and argument on the test selection for the pilot study that we have performed on different types of waste materials. Test results are presented in a second paper.As the application of many of the proposed test methods is new in the field of waste management, the principles of the tests are described. The selected tests tackle important hazardous properties but refinement of the test battery is needed to fulfil the a priori conditions.     

Formation of recycled plastics from depolymerized monomers derived from waste fiber-reinforced plastics

To develop a new method for the chemical recycling of plastics, we examined the formation of recycled polymers from the recovered monomeric materials of solubilized waste fiber-reinforced plastics (FRP) under supercritical alcoholic conditions. Treatment of waste FRP with supercritical MeOH resulted in the formation of monomeric organic compounds that mainly contained dimethyl phthalate (DMP) and propylene glycol. The presence of these materials was confirmed by gas chromatography and nuclear magnetic resonance analyses and they were mixed with new DMP and glycols in various ratios to form unsaturated polyesters. The polymerization progressed successfully for all mixing ratios of the recovered and new DMP. Hardness tests on these recycled polymers indicated that the polymer made from a 1:1 mixture of recovered and new dimethyl phthalate had almost the same level of hardness as the polymers made from new materials. We also examined the formation of recycled FRP by using glass fibers and monomeric materials recovered through the present depolymerization method. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

A Study on Benzoylation and Graft Copolymerization of Lignocellulosic Cannabis indica Fiber

Present work deals with the surface modification of Cannabis indica fiber through benzoylation and graft copolymerization of acrylonitrile (AN) onto C. indica fibers under the influence of microwave radiations. The Benzoylation of C. indica fiber was carried out by treating raw fiber with varying concentrations of benzoyl chloride solution. Different reaction parameters for graft copolymerization, such as reaction time, initiator concentration, nitric acid concentration, pH and monomer concentration were optimized to get the maximum percentage of grafting (25.54%). A suitable mechanism to explain benzoylation and graft copolymerization has been also proposed. Raw C. indica fiber, graft copolymerized and benzoylated fibers were subjected to evaluation of some of their properties like swelling behavior, moisture absorbance and resistance towards chemicals. Cannabis indica fibers treated with 5% benzoyl chloride solution and AN graft copolymerized fibers have been found to show more resistant towards moisture, water and chemicals when compared with that of untreated fibers. Morphological, structural changes, thermal stability and crystallanity of raw, graft copolymerized and benzoylated fibers have also been studied by SEM, FTIR, TGA and XRD techniques. It has been observed that the crystallinity of fiber decreases but thermal stability increases on surface modification.     

Validation of Microtox as a first screening tool for waste classification

The Waste Framework Directive (WFD; 2008/98/EG) describes how waste materials are to be classified as hazardous or not. For complex waste materials chemical analyses are often not conclusive and the WFD provides the possibility to assess the hazardous properties by testing on the waste materials directly. As a methodology WFD refers to the protocols described in the CLP regulation (regulation on Classification, Labeling and Packaging of chemicals) but the toxicity tests on mammals are not acceptable for waste materials. The DISCRISET project was initiated to investigate the suitability of alternative toxicity tests that are already in use in pharmaceutical applications, for the toxicological hazard assessment of complex waste materials. Results indicated that Microtox was a good candidate as a first screening test in a tiered approached hazard assessment. This is now further validated in the present study. The toxic responses measured in Microtox were compared to biological responses in other bioassays for both organic and inorganic fractions of the wastes. Both fractions contribute to the toxic load of waste samples. Results show that the Microtox test is indeed a good and practical screening tool for the organic fraction. A screening threshold (ST) of 5 geq/l as the EC₅₀ value in Microtox is proposed as this ST allows to recognize highly toxic samples in the screening test. The data presented here show that the Microtox toxicity response at this ST is not only predictive for acute toxicity in other organisms but also for sub lethal toxic effects of the organic fraction. This limit value has to be further validated. For the inorganic fraction no specific biotest can be recommended as a screening test, but the use of direct toxicity assessment is also preferable for this fraction as metal speciation is an important issue to define the toxic load of elutriate fractions. A battery of 3 tests (Microtox, Daphnia and Algae) for direct toxicity assessment of this fraction is recommended in literature, but including tests for mechanistic toxicity might be useful.     

Improving the Rheological and Mechanical Properties of Recycled PET Modified by Macromolecular Chain Extenders Synthesized by Controlled Radical Polymerization

In this work, a series of reactive copolymers of glycidyl methacrylate (G), styrene (S) and acrylonitrile (AN), were synthesized through reversible addition-fragmentation chain transfer polymerization and evaluated as macromolecular chain extenders in reactive extrusion of recycled poly(ethylene terephthalate) (rPET). The results obtained indicate that the addition of the reactive copolymers as chain extenders modifies the chain conformation in rPET causing low crystallization rate and low crystallinity. The physical and rheological properties (melt flow and intrinsic viscosity) of chain-extended rPET improved, rendering better processability. rPET modified with polymeric chain extenders shows improved rheological properties (complex viscosity, storage and loss modulus) and also displays higher elongation at break and impact properties as the GMA content in the chain extenders increase.     

Odor Control for Land Application of Lime Stabilized Biosolids

Over three million dry metric tons of biosolids produced in the United States are land applied as Class B. Lime stabilization is employed for biosolids treatment at approximately 20% of the wastewater treatment plants because it is a simple and inexpensive process. During lime stabilization, the pH of sewage sludge is raised above 12 for pathogen inactivation and odor reduction. Lime dose and mixing have been found to greatly reduce odor generation from lime stabilized biosolids. A better quality biosolids product is less likely to create public opposition to land application programs. In this study, land application tests using Class B biosolids were conducted in order to determine whether better mixing can reduce odor generation during the land application of lime stabilized biosolids. The mixing quality of a treatment plant’s lime stabilized biosolids was improved by relocating the lime addition point, which prolonged the mixing time and produced a better mixed biosolids product. Based on field observations of land application, the poorly mixed biosolids were more odorous and offensive prior to incorporation. However, once incorporated into the soil, there was no appreciable odor difference between the biosolids. Another land application study was conducted to assess the odor of unincorporated Class A biosolids and compare it with incorporated Class A biosolids with the soil.     

GHS化学品危险性分类及其公示要素(下)

概述了全球化学品统一分类和标签制度（GHS）的产生背景、推行GHS的重要意义，介绍了GHS关于化学品危险性分类和公示要素的主要内容，评估了我国现行化学品危险性分类与GHS分类的差异点，并对我国全面实施GHS提出了若干对策建议。     

Population dynamics during startup of thermophilic anaerobic digesters: The mixing factor

Two thermophilic digesters were inoculated with manure and started-up under mixed and stagnant conditions. The Archaea in the mixed digester (A) were dominated by hydrogenotrophic Methanobateriaceae (61%) with most of the methane being produced via syntrophic pathways. Methanosarcinales (35%) were the only acetoclastic methanogens present. Acetate dissipation seems to depend on balanced hydrogenotrophic-to-acetotrophic abundance, which in turn was statistically correlated to free ammonia levels. Relative abundance of bacterial community was associated with the loading rate. However, in the absence of mixing (digester B), the relationship between microbial composition and operating parameters was not discernible. This was attributed to the development of microenvironments where environmental conditions are significantly different from average measured parameters. The impact of microenvironments was accentuated by the use of a non-acclimated seed that lacks adequate propionate degraders. Failure to disperse the accumulated propionate, and other organics, created high concentration niches where competitive and inhibiting conditions developed and favored undesired genera, such as Halobacteria (65% in B). As a result, digester B experienced higher acid levels and lower allowable loading rate. Mixing was found necessary to dissipate potential inhibitors, and improve stability and loading capacity, particularly when a non-acclimated seed, often lacking balanced thermophilic microflora, is used.     

GHS化学品危险性分类及其公示要素(上)

概述了全球化学品统一分类和标签制度（GHS）的产生背景、推行GHS的重要意义，介绍了GHS关于化学品危险性分类和公示要素的主要内容，评估了我国现行化学品危险性分类与GHS分类的差异点，并对我国全面实施GHS提出了若干对策建议。     

Hardening performance of reclaimed gypsums for stabilizing agent to improve soft clayey ground

For a prospective solution of effective recycling of gypsum board wastes, the present study was conducted to evaluate applicability of reclaimed gypsum as stabilizing agent for improvement of soft clayey ground. A series of unconfined compression tests and needle penetration tests were conducted to understand the fundamental properties of reclaimed gypsum and gypsum treated soils and the durability in water. An important finding was strength decrease in relation to mixing time of gypsum and soil. This may attribute to excessive mixing that caused breakage of the promptly hardened gypsum treated clay. In addition, from sounding and laboratory tests on the stabilized ground by shallow mixing method with different execution conditions, it was found that the strength of stabilized ground appeared in an early stage and that the hardening effect of cement that was used in combination with gypsum continued in a longer period. Regarding an environmental aspect, a specific amount of cement could have restrained leaching fluorine satisfactorily under the standard level in the field by adopting suitable mixing proportions based on the laboratory mixing test results. For practical application, the mixing procedure was a major factor of strength growth when hemihydrate gypsum was used to stabilize soft clayey ground.     

Ecotoxicological characterisation of 12 incineration ashes using 6 laboratory tests

In the European Waste List (2000/532/EC as amended) the ash of municipal waste incineration is defined as a so called mirror entry. This waste can be classified as hazardous or non-hazardous depending on the content of hazardous substances and other risk properties. For the assignment of waste in mirror entries, 14 criteria are defined. One of the criteria is H14 “ecotoxic”. In the presented study, the ecotoxicological potential of 12 ashes from different incineration plants has been assessed using biological test systems. The test battery included aquatic tests with eluates (algae, daphnids, and luminescent bacteria) and terrestrial tests with solid waste (plants, earthworms and bacteria). The test results revealed a clear ecotoxicological hazard potential for some of the MWI ashes. Despite the fact that fresh ashes were several times more toxic than aged ashes both groups did not differ consistently in terms of toxicity. The results show also that there is no correlation between the biological effects and the analyzed chemical compounds of the ash samples.     

新型无机复合混凝剂的制备及脱色效果研究

了以铝厂赤泥为原料制备无机复合凝凝剂的工艺,以制备过程中酸溶尼所用的盐酸浓度、酸溶时间和聚合ＰＨ等进行了优化。直接耐酸大红溶液和分散黄溶液的脱色以试验结果表明,此种混凝剂的脱色效果优于聚合氯化铝和聚合硫酸铁。     

Reactively Compatibilized Cellulosic Polylactide Microcomposites

Poly(lactic acid) (PLA) possesses a suite of favorable material properties that are enabling its penetration into diverse markets (e.g., as packaging material or textile fibers). In order to increase the range of applications for this material, it is necessary to modify its properties and for certain applications, reduce its cost. The introduction of fibers into a polymeric matrix is an established route towards property enhancement provided good dispersion and intimate interfacial adhesion can be achieved. In addition, cellulosic microfibers are obtainable at low to moderate cost. In this study, reactive compatibilization of cellulosic fibers with PLA is pursued. Hydroxyl groups available on the surface of cellulosic fibers are used to initiate lactide polymerization. Various processing strategies are investigated: (1) blending preformed PLA with the fiber material, (2) through a one-step process in which lactide is polymerized in the presence of the fibers alone, or (3) reactive compatibilization in the presence of preformed high molecular weight polymer. The results show that materials prepared by simultaneous introduction of lactide and preformed high molecular PLA at the beginning of the reaction possess superior mechanical properties compared to composites made by either purely mechanical mixing or solely polymerization of lactide in the presence of fibers. The modulus of materials containing 25% fibers which are prepared by reactive compatibilization of 30% preformed PLA and 70% lactide (30/70 P/L) improves by 53% compared to the homopolymer, whereas 36% reinforcement can be achieved upon purely mechanical mixing. A further increase to 35% fiber loading leads to a reduction in modulus due to an excess in initiating groups. The same trend was observed in systems containing 65% preformed PLA and 35% lactide (65/35 P/L) with an overall achievable reinforcement that was slightly lower.     

非离子型聚丙烯酰胺絮凝剂的制备及其絮凝性能

以丙烯酰胺（AM）和烷基酚聚醚（APAP）为单体，采用反相乳液聚合法制备了流动性好的非离子型聚丙烯酰胺絮凝剂（PAM-APAP）。考察了乳化剂和引发剂的种类、单体总质量分数、单体配比和反应温度等因素对聚合反应的影响。实验结果表明，制备PAM-APAP的最佳工艺条件为：单体总质量分数35%、m（AM）∶m（APAP）=9.0∶1.0、Span80+Tween80复配乳化剂加入量为油水总质量的7%、m（Span80）∶m（Tween80）=7.0∶1.5、V50加入量为单体总质量的1.5‰、反应温度50℃。PAM-APAP具有较好的絮凝效果，与其他絮凝剂相比用量较少，在加入量为100mg/L时，对聚合物驱油中产生的含聚合物污水的浊度去除率为87.9%，去油率为89.5%，且絮体不黏壁。     

Physical impact of waterjet‐based sediment remediation on benthic organisms

Adding activated carbon to sediments has been shown to be an effective means of reducing the bioavailability of certain contaminants. The current state of the practice is to mechanically mix activated carbon to a target concentration of 3 percent at depths of approximately 30 cm using a rotovator or similar construction equipment. Waterjets have been used to cut hard material using a mixture of water and an abrasive. If activated carbon is substituted for the abrasive, waterjets have the potential to use surface injection as a replacement for mechanical mixing during sediment remediation. A perceived benefit of waterjet‐based sediment remediation is that there may be a reduced potential for benthic organism mortality related to amendment delivery. A set of waterjet parameters were identified that have the potential to achieve amendment placement goals, and a series of waterjet tests were conducted to evaluate the potential impact on the benthic community. The tests included mortality testing using a swimming macroinvertebrate and a burrowing invertebrate, benthic artifacts such as shells, and craft foam as a surrogate for living organisms. The results indicated that the immediate survivability was typically greater than 50 percent, and that empirical relationships between two variables (waterjet nozzle diameter and the water column height between the nozzle and the target) and the depth of cut in the foam could be established. Data are not available in the literature for direct comparison of organism survivability immediately after mechanical mixing, but the results of this study provide motivation for the further evaluation of waterjets on the basis of the low observed mortality rates. Future waterjet work may address field‐scale characterization of mixing effectiveness, resuspension potential, technical feasibility, and cost. © 2011 Wiley Periodicals, Inc.     

Improvement of permeability of waste sludge by mixing with slag or construction and demolition waste

To determine the allowable ratio of waste sludge required to ensure an aerobic zone in the landfill, we investigated sludge permeability, which involved mixing sludge, the major landfill waste in Japan, at different mixing ratios with other wastes (slag and construction and demolition waste (C&D)). We measured parameters of sample permeability and analyzed parameters that exert a large influence on oxygen penetration depth with a simulation model accounting for both diffusion and convection driven by temperature gradients. We also determined the critical volumetric contents in which gas and/or water permeability change significantly when sludge is mixed with sand or gravel. From the results of the simulations, gas permeability of the layer, the difference between inside and outside temperatures and the oxygen consumption rate exert a large influence on the resulting oxygen penetration depth. The allowable ratio of sludge required to ensure an aerobic zone in the landfill was determined by considering the balance of the above three parameters. By keeping volumetric sludge content to below 25%, air convection and oxygen penetration depth of several meters were achieved in the modeling.     

Eco-Compatible Use of Olive Husk as Filler in Thermoplastic Composites

A study on the possibility of recycling waste materials, such as olive husk, the solid phase derived from an olive oil mill, in blend with thermoplastic polymers to produce new materials for manufacturer of, for example, containers and formworks, has been carried out. The present paper describes the methodology used for the preparation and the characterization of composite samples prepared by mixing various percentages of olive husk and polypropylene. A screening on the chemical-physical characteristics of the olive husk is reported, as well as a set of tests applied to evaluate the mechanical properties of the manufactured products obtained.     

BMP tests of source selected OFMSW to evaluate anaerobic codigestion with sewage sludge

The aim of this study is to characterize different types of source selected organic fraction of municipal solid waste (SS-OFMSW) in order to optimize the upgrade of a sewage sludge anaerobic digestion unit by codigestion. Various SS-OFMSW samples were collected from canteens, supermarkets, restaurants, households, fruit–vegetable markets and bakery shops. The substrates characterization was carried out getting traditional chemical–physical parameters, performing elemental analysis and measuring fundamental anaerobic digestion macromolecular compounds such as carbohydrates, proteins, lipids and volatile fatty acids. Biochemical methane potential (BMP) tests were conducted at mesophilic temperature both on single substrates and in codigestion regime with different substrates mixing ratios. The maximum methane yield was observed for restaurant (675 NmlCH₄/gVS) and canteens organic wastes (571 and 645 NmlCH₄/gVS). The best codigestion BMP test has highlighted an increase of 47% in methane production respect sewage sludge digestion.     

Tests for the evaluation of ammonium attenuation in MSW landfill leachate by adsorption into bentonite in a landfill liner

Uncontrolled leachate emissions are one of the key factors in the environmental impact of municipal solid waste (MSW) landfills. The concentration of ammonium, given the anaerobic conditions in traditional landfills, can remain significantly high for a very long period of time, as degradation does not take place and volatilisation is not significant (the pH is not high enough to considerably shift the equilibrium towards un-ionised ammonia). Recent years have witnessed a continuous enhancement of landfill technology in order to minimize uncontrolled emissions into the environment; bottom lining systems have been improved and more attention has been devoted to the study of the attenuation of the different chemicals in leachate in case of migration through the mineral barrier. Different natural materials have been considered for use as components of landfill liners in the last years and tested in order to evaluate the performance of the different alternatives. Among those materials, bentonite is often used, coupled with other materials in two different ways: in addition to in situ soil or in geocomposite clay liner (GCL). A lab-scale test was carried out in order to further investigate the influence of bentonite on the attenuation of ammonium in leachate passing through a landfill liner. Two different tests were conducted: a standardized batch test with pulverized bentonite and a batch test with compacted bentonite. The latter was proposed in order to better simulate the real conditions in a landfill liner. The two tests produced values for the partition coefficient K(d) higher than the average measured for other natural materials usually utilized as components of landfill liners. Moreover, the two tests showed similar results, thus providing a further validation of the suitability of the standard batch test with pulverized bentonite. A thorough knowledge of attenuation processes of ammonium in landfill liners is the basis for the application of risk analysis models for the evaluation of the failure of bottom liners or their components.     

美国高产量化学品数据库在筛选优先化学品中的应用

介绍了美国高产量(HPV)化学品数据库的内容、格式和发展情况，以及采用HPV化学品数据筛选优先化学品的程序。HPV化学品数据库主要包括化学品数据、化学品毒性特征描述、优先风险评估以及数据资助方、提交方及测试方的相关信息，支持物质名称或化学文摘社登记号搜索。采用HPV化学品数据可通过自动分类、毒性特征描述和风险优先等级评价三级筛选程序筛选优先化学品。