Hazard property classification of waste according to the recent propositions of the EC using different methods

Hazard classification of waste is a necessity, but the hazard properties (named “H” and soon “HP”) are still not all defined in a practical and operational manner at EU level. Following discussion of subsequent draft proposals from the Commission there is still no final decision. Methods to implement the proposals have recently been proposed: tests methods for physical risks, test batteries for aquatic and terrestrial ecotoxicity, an analytical package for exhaustive determination of organic substances and mineral elements, surrogate methods for the speciation of mineral elements in mineral substances in waste, and calculation methods for human toxicity and ecotoxicity with M factors.In this paper the different proposed methods have been applied to a large assortment of solid and liquid wastes (>1 0 0).Data for 45 wastes – documented with extensive chemical analysis and flammability test – were assessed in terms of the different HP criteria and results were compared to LoW for lack of an independent classification. For most waste streams the classification matches with the designation provided in the LoW. This indicates that the criteria used by LoW are similar to the HP limit values.This data set showed HP 14 ‘Ecotoxic chronic’ is the most discriminating HP. All wastes classified as acute ecotoxic are also chronic ecotoxic and the assessment of acute ecotoxicity separately is therefore not needed. The high number of HP 14 classified wastes is due to the very low limit values when stringent M factors are applied to total concentrations (worst case method). With M factor set to 1 the classification method is not sufficiently discriminating between hazardous and non-hazardous materials. The second most frequent hazard is HP 7 ‘Carcinogenic’. The third most frequent hazard is HP 10 ‘Toxic for reproduction’ and the fourth most frequent hazard is HP 4 “Irritant – skin irritation and eye damage”. In a stepwise approach, it seems relevant to assess HP 14 first, then, if the waste is not classified as hazardous, to assess subsequently HP 7, HP 10 and HP 4, and then if still not classified as hazardous, to assess the remaining properties.The elements triggering the HP 14 classification in order of importance are Zn, Cu, Pb, Cr, Cd and Hg. Progress in the speciation of Zn and Cu is essential for HP 14. Organics were quantified by the proposed method (AFNOR XP X30-489) and need no speciation. Organics can contribute significantly to intrinsic toxicity in many waste materials, but they are only of minor importance for the assessment of HP 14 as the metal concentrations are the main HP 14 classifiers. Organic compounds are however responsible for other toxicological characteristics (hormone disturbance, genotoxicity, reprotoxicity…) and shall be taken into account when the waste is not HP 14 classified.     

烟草废弃物快速堆肥过程中重金属Cd形态变化特征

以烟草废弃物为原料,活性土壤为载体建立堆体,研究重金属镉的形态变化,及堆肥过程中的动态变化规律。结果表明,烟草废弃物与活性土壤混合能快速腐熟。堆肥总质量下降,重金属镉含量相对增加。重金属镉的铁锰氧化态比例增加19%,有机结合态比例在堆肥升温阶段增加,腐熟后有所下降。残渣态比例大幅度上升,增加达到5倍,且在腐熟阶段增幅最大。说明堆肥处理有利于降低重金属镉的活性。     

Investigation of trace metal binding properties of lignin by diffusive gradients in thin films

The binding behavior of lignin for Pb, Cu, Co, Mn, Cd and Ni was studied using the diffusive gradients in thin films technique (DGT). Samplers with different structures of diffusive gel were used in the well-stirred systems containing known concentrations of metals along with (a) 10, 20 and 40 μM lignin and; (b) 0.64 and 6.47 μM Suwannee river fulvic acid + 40 μM lignin at an ionic strength of 0.01 M (NaNO₃) and pH = 7. Diffusion coefficients of lignin complexes in acrylamide gels were estimated and found to be less than 5% of the equivalent coefficients for the uncomplexed metal ions. These values were used to calculate concentrations of labile metals from DGT measurements in solutions, where lignin could discriminate metals in the order of Pb⁺² > Cu⁺² > Cd⁺² > Ni⁺² > Co⁺² > Mn⁺². Stability constants (Log K) were calculated using Visual MINTEQ II and WHAM V software. The K values were compared with the stability constants from titration of Pb and Cd with 10 μM lignin aqueous samples and with those of humic substances in natural waters. The constants obtained from measurement of complexing capacities might bias the real corresponding values unless two line regression analyses on titration data are considered. The DGT study of fractionation of metal species at varying ratios indicated that the proportion of organic complexes decreased with increasing ratios and gradually more metals were exchanged with inorganic phases. Speciation of Pb and Cd is affected by the concentrations of FA, Cd is dominantly bound with FA while Pb is evenly partitioned between the ligands. The comprehensive knowledge of metal-lignin complexes sheds some light on in situ operational speciation information that can be achieved by DGT.     

Inorganic and methyl-mercury speciation in sediments of the Swarzędzkie Lake

Sediment samples were analysed for mercury and methylmercury content in different parts of the bottom sediment of Swarz ?dzkie Lake, which were influenced by different external pollution sources. The results of determination with two methods of mineralization using two separate media (HNO₃/H₂O₂ and HF) were compared. The accuracy of the studied methods was analysed using certified reference material IAEA 405 of river sediment. The recovery of mercury was satisfactory and ranged from 97.5 to 98.8%. Methylmercury compounds in the studied sediments were found in limited concentrations. Their concentrations ranged from 0.26 to 58.1 μg kg^?1, i.e. 1.0–7.4% of the total mercury content. The depth profile displayed high values of both total and methylmercury content at a depth of 10–20 cm, related to the heavy pollution of the lake in the 1980s. Canonical analysis displayed the relationship of both total mercury and methylmercury concentrations with organic matter and phosphorus content in bottom sediments.     

Temporal patterns of atmospheric mercury species in northern Mississippi during 2011–2012: Influence of sudden population swings

Gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate bound mercury (PBM) were measured on the University of Mississippi campus from July 2011 to June 2012. It is believed to be the first time that concentrations of atmospheric mercury species have been documented in northern Mississippi, and at a location with relatively large and sudden swings in population. The mean concentration (±1SD) of GEM was 1.54 ± 0.32 ng m⁻³; levels were lower and generally more stable during the winter (1.48 ± 0.22) and spring (1.46 ± 0.27) compared with the summer (1.56 ± 0.32) and fall (1.63 ± 0.42). Mean concentrations for GOM and PBM were 3.87 pg m⁻³ and 4.58 pg m⁻³, respectively; levels tended to be highest in the afternoon and lowest in the early morning hours. During the fall and spring academic semesters concentrations and variability of GOM and PBM both increased, possibly from vehicle exhaust. There were moderate negative correlations with wind speed (all species) and humidity (GOM and PBM). Backward air mass trajectory modeling for the ten highest peaks for each mercury species revealed that the majority of these events occurred from air masses that passed through the northern continental US region. Overall, this study illustrates the complexity of temporal fluctuations of airborne mercury species, even in a small town environment.     

Sequential Extraction Versus Comprehensive Characterization of Heavy Metal Species in Brownfield Soils

The applicability of sequential extraction as a means to determine species of heavy-metals was examined by a study on soil samples from two Superfund sites: the National Lead Company site in Pedricktown, NJ, and the Roebling Steel, Inc., site in Florence, NJ. Data from a standard sequential extraction procedure were compared to those from a comprehensive study that combined optical- and scanning-electron microscopy, X-ray diffraction, and chemical analyses. The study shows that larger particles of contaminants, encapsulated contaminants, and/or man-made materials such as slags, coke, metals, and plastics are subject to incasement, non-selectivity, and redistribution in the sequential extraction process. The results indicate that standard sequential extraction procedures that were developed for characterizing species of contaminants in river sediments may be unsuitable for stand-alone determinative evaluations of contaminant species in industrial-site materials. However, if employed as part of a comprehensive, site-specific characterization study, sequential extraction could be a very useful tool.     

Association of plutonium with sediments from the Ob and Yenisey Rivers and Estuaries

The present study applied sequential extraction techniques to investigate the binding and mobility of plutonium (Pu) in sediments from the rivers and estuaries of the Ob and Yenisey. As a study site, the Ob and Yenisey are particularly interesting as both rivers have weapons-grade Pu sources in their catchment areas, including the Russian Pu production and reprocessing plants at Mayak, Tomsk-7 and Krashnoyarsk, and the Semipalantinsk nuclear weapons testing site in Kazakhstan. Plutonium activity and ²⁴⁰Pu/²³⁹Pu ratios were determined using accelerator mass spectrometry (AMS). Sequential extractions showed that between 47 and 80% of the Pu in Yenisey River sediments and 35–53% of the Pu in soils around the Techa River are mobilized with weak oxidising agents, which can indicate that Pu is bound to organic material. In contrast, Pu in Ob and Yenisey Estuarine sediments was more strongly bound, with 60–100% being found in the HNO₃-extractable fraction. This change in speciation could reflect either that Pu bound to organic material in the Techa and Yenisey River sediments becomes more fixed to the sediments with time, or that organic-bound Pu is mobilized and released to the water when the sediments encounter the more saline water of the Ob and Yenisey estuaries. In general, ²⁴⁰Pu/²³⁹Pu ratios were relatively consistent between different extraction fractions, although, in whole sediments, an increase in ratio was observed with distance from the source. This reflects the increased influence of weapon fallout from catchment runoff within the river systems, as compared to the weapons-grade sources close to the production and reprocessing plants. Knowledge of Pu speciation in the Ob and Yenisey Rivers, and the processes controlling its behaviour in estuarine systems, can improve predictions of its transfer and subsequent environmental impact to Arctic Seas.     

Arsenic species in ecosystems affected by arsenic-rich spring water near an abandoned mine in Korea

The objectives of this study were to quantitatively estimate the distribution of arsenic with its speciation and to identify potential pathways for transformation of arsenic species from samples of water, sediments, and plants in the ecosystem affected by the Cheongog Spring, where As(V) concentration reached levels up to 0.270 mg L⁻¹. After flowing about 100 m downstream, the arsenic level showed a marked reduction to 0.044 mg L⁻¹ (about 84% removal) without noticeable changes in major water chemistry. The field study and laboratory hydroponic experiments with the dominant emergent plants along the creek (water dropwort and thunbergian smartweed) indicated that arsenic distribution, reduction, and speciation appear to be controlled by, (i) sorption onto stream sediments in exchangeable fractions, (ii) bioaccumulation by and possible release from emergent plants, and (iii) transformation of As(V) to As(III) and organic species through biological activities.     

Source characterization of ambient fine particles at multiple sites in the Seattle area

To identify major PM_2.5 (particulate matter ≤2.5 μm in aerodynamic diameter) sources with a particular emphasis on the ship engine emissions from a major port, integrated 24 h PM_2.5 speciation data collected between 2000 and 2005 at five United State Environmental Protection Agency's Speciation Trends Network monitoring sites in Seattle, WA were analyzed. Seven to ten PM_2.5 sources were identified through the application of positive matrix factorization (PMF). Secondary particles (12–26% for secondary nitrate; 17–20% for secondary sulfate) and gasoline vehicle emissions (13–31%) made the largest contributions to the PM_2.5 mass concentrations at all of the monitoring sites except for the residential Lake Forest site, where wood smoke contributed the most PM_2.5 mass (31%). Other identified sources include diesel vehicle emissions, airborne soil, residual oil combustion, sea salt, aged sea salt, metal processing, and cement kiln. Residual oil combustion sources identified at multiple monitoring sites point clearly to the Port of Seattle suggesting ship emissions as the source of oil combustion particles. In addition, the relationship between sulfate concentrations and the oil combustion emissions indicated contributions of ship emissions to the local sulfate concentrations. The analysis of spatial variability of PM_2.5 sources shows that the spatial distributions of several PM_2.5 sources were heterogeneous within a given air shed.     

Females learn from mothers and males learn from others. The effect of mother and siblings on the development of female mate preferences and male aggression biases in Lake Victoria cichlids, genus Mbipia

While species-assortative behaviour is often observed in sympatrically occurring species, there are few examples where we understand the extent to which development of assortative behaviour is genetically or environmentally determined, for instance, through learning. However, the majority of mate choice theory assumes genetic recognition mechanisms. Knowledge about the development of species recognition is important for our understanding of how closely related species can coexist and how this coexistence may have arisen. The ontogeny of female mate choice, for instance, may critically influence the degree of assortative mating under many circumstances. Also, male assortative aggression behaviour may affect fitness and the possibility for coexistence of two closely related species. Here, we test whether male aggression biases and female mate preferences of two Lake Victoria rock cichlid species, Mbipia mbipi and Mbipia lutea, are affected by experience. With an interspecific cross-fostering experiment, we test for the effect of experience with the phenotype of the mother and that of the siblings on species-assortative mate preferences and aggression biases. We demonstrate that female mate preferences are strongly influenced by learning about their mothers’ phenotype but not by experience with their siblings, despite ample opportunity for interactions. Male aggression biases, in contrast, are affected by experience with siblings but not by learning about their mothers’ phenotype. We suggest that the development of assortative behaviour of females, but not of males, creates favourable conditions for sympatric speciation in Lake Victoria cichlids.