The use of extraction chromatography resins to concentrate actinides and strontium from soil for radiochromatographic analyses

An analytical technique utilizing selective extractant resins to concentrate strontium and actinides from soil followed by separation with radiochromatography was evaluated. The technique was tested using uncontaminated soil samples spiked with a radionuclide tracer solution that were either microwave-aided acid digested or leached with a strong acid. Extraction of the strontium and actinides from the acidified solution was accomplished using a serial arrangement of Sr-Resin and TRU-Resin columns. The combined eluate solutions from the extraction resins were treated with HNO(3) and H(2)O(2) to oxidize residual extractant and eluates prior to separation and analysis of the radionuclides by radiochromatography. Chromatograms obtained with larger soil mass loadings resulted in either incomplete peak resolution of the tracers or had highly variable peak elution times, indicative of an ionic interfering constituent(s). Better separations (e.g., chromatograms that resolved all radioactive constituents) were obtained when the sample mass loading was decreased, but with a concurrent decreased sensitivity for the radionuclides. Elemental analyses of the soil were conducted to provide data on the ionic constituents in unprocessed soil and post-processed soil samples. These results identified aluminum as an interfering contributor to the poor performance exhibited by the radiochromatographic separations.     

Initial Stages of Recovery of Soil Macrofauna Communities after Reduction of Emissions from a Copper Smelter

Analysis of natural recovery of communities after reduction of industrial emissions is important for gaining an insight into their stability. However, there is obvious deficit in observations on the course of this recovery; in particular, no data on direct comparisons of the state of communities before and after reduction of emissions are available for soil macroinvertebrates. We have studied the structure of soil macrofauna communities at the level of supraspecific taxa in southern taiga spruce-fir forests in the region exposed to emissions from the Middle Ural Copper Smelter (MUCS; Revda, Sverdlovsk oblast). The data over three periods—high, reduced, and almost terminated emissions (1990–1991, 2004, and 2014–2016, respectively)—have been compared to test the hypothesis that the communities do not recover rapidly. The results partly confirm this hypothesis. On the one hand, the response of pedobionts to pollution at a qualitative level has remained basically unchanged: in each of the three periods, their total abundance (and that of the majority of groups) decreased abruptly as the MUCS was approached, with dominance shifting from saprophages to phyto- and zoophages. On the other hand, signs of recovery have appeared during the last period: the abundance of pedobionts has increased, and pollution-sensitive groups (earthworms, enchytraeids, and mollusks) have approached closer to the MUCS. This is most likely explained by decrease in the toxicity of metals due to normalization of soil pH. Rapid recolonization of defaunated territory may be accounted for by the presence in it of microsites with more favorable conditions, compared to the surrounding area, which allow low-mobile forms to survive beyond the boundaries of their main distribution area.

     

Bioaccumulation of PCDD/Fs,PCBs and PBDEs by earthworms in field soils of an E-waste dismantling area in China

A total of 60 paired samples of earthworm, corresponding soil and wormcast were collected to investigate the bioaccumulation tendency of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in earthworms from a typical E-waste dismantling area in east China. Significant correlations were observed for the total concentrations among different matrix types except for PCDD/Fs in soil and earthworm. The bioaccumulation tendency showed some differences among the contaminants. Calculated biota–soil accumulation factors (BSAFs) indicated that PCBs and PBDEs had higher bioaccumulation potential compared to PCDD/Fs, which was somewhat different from laboratory studies. The plot of mean BSAFs versus log K_ow values for PCBs and PBDEs was well fitted by a second-order polynomial with the maximum BSAF at approximately log K_ow of 6.5. While for PCDD/Fs, only a slightly decreasing trend was observed with increasing log K_ow. Composition analysis indicated that tetra-, penta- and hexa-halogenated homologs had higher bioaccumulation levels, indicating that medium-halogenated congeners with log K_ow around 6.5 are more easily accumulated by earthworms. Furthermore, the ratios of BDE-47/-99 and BDE-99/-100 showed some discrepancies with the technical products and other biotic species, suggesting different bioaccumulation potential of PBDEs in earthworm.     

Diffusive gradient in thin FILMS (DGT) compared with soil solution and labile uranium fraction for predicting uranium bioavailability to ryegrass

The usefulness of uranium concentration in soil solution or recovered by selective extraction as unequivocal bioavailability indices for uranium uptake by plants is still unclear. The aim of the present study was to test if the uranium concentration measured by the diffusive gradient in thin films (DGT) technique is a relevant substitute for plant uranium availability in comparison to uranium concentration in the soil solution or uranium recovered by ammonium acetate. Ryegrass (Lolium perenne L. var. Melvina) is grown in greenhouse on a range of uranium spiked soils. The DGT-recovered uranium concentration (C_DGT) was correlated with uranium concentration in the soil solution or with uranium recovered by ammonium acetate extraction. Plant uptake was better predicted by the summed soil solution concentrations of UO₂²⁺, uranyl carbonate complexes and UO₂PO₄⁻. The DGT technique did not provide significant advantages over conventional methods to predict uranium uptake by plants.     

Sorption-desorption tests to assess the risk derived from metal contamination in mineral and organic soils

We obtained the sorption isotherms of Cd, Cu, Pb and Zn from seven soils with contrasting properties, including mineral and organic soils. The distribution coefficients (Kd) were determined from batch tests in a solution that simulated the soil solution cationic composition. The Kd values of the target metals varied greatly depending on soil type and initial metal concentration. Sorption isotherms were fitted to Freundlich and Langmuir models, and derived parameters were correlated to soil properties through the construction of a correlation matrix and application of Principal Component Analysis. The batch Kd showed a satisfactory agreement with the Kd obtained from field-contaminated soils. The sorption tests were complemented with the estimation of the reversibility of metal sorption by the application of an extraction test. The extraction yields, which did not relate to the initial metal concentration, depended on the metal-soil combination, and showed no correlation to batch Kd values. The risk derived from a contamination event was estimated through the quantification of a Retention Factor, defined as the ratio of the Kd versus the extraction yield. Results showed that this was an excellent index to highlight which metal and soil represent the most vulnerable scenarios after a contamination event.     

226Ra/238U disequilibrium in an upland organic soil exhibiting elevated natural radioactivity

This paper presents the results of a study into the anomalous 226Ra/238U disequilibrium (226Ra/238U of 0.5-9) exhibited by an upland organic soil in Co. Donegal, Ireland. Radiochemical speciation of 226Ra, 238U and 225Ra indicates that in this organic soil the high 226Ra/238U ratio is due to loss of 235U relative to 226Ra via oxidation and mobilisation of 238U in the upper layers of the soil and subsequent loss in solution. At the lower, more reducing depths of the soil profile, 238U and 226Ra are essentially in equilibrium. Loss of 238U appears to occur primarily from the easily oxidised organic and iron oxide fractions of the soil, samples exhibiting high 226Ra/238U ratios displaying significantly lower 238U levels in these fractions than samples whose ratio is below the average value for the soil of the valley. Selective enrichment of 226Ra by plants or preferential leaching of 226Ra from the underlying rock is not supported by the results of this study.     

Differences in U root-to-shoot translocation between plant species explained by U distribution in roots

Accumulation and distribution of uranium in roots and shoots of four plants species differing in their cation exchange capacity of roots (CECR) was investigated. After exposure in hydroponics for seven days to 100 μmol U L⁻¹, distribution of uranium in roots was investigated through chemical extraction of roots. Higher U concentrations were measured in roots of dicots which showed a higher CECR than monocot species. Chemical extractions indicated that uranium is mostly located in the apoplasm of roots of monocots but that it is predominantly located in the symplasm of roots of dicots. Translocation of U to shoot was not significantly affected by the CECR or distribution of U between symplasm and apoplasm. Distribution of uranium in roots was investigated through chemical extraction of roots for all species. Additionally, longitudinal and radial distribution of U in roots of maize and Indian mustard, respectively showing the lowest and the highest translocation, was studied following X-ray fluorescence (XRF) analysis of specific root sections. Chemical analysis and XRF analysis of roots of maize and Indian mustard clearly indicated a higher longitudinal and radial transport of uranium in roots of Indian mustard than in roots of maize, where uranium mostly accumulated in root tips. These results showed that even if CECR could partly explain U accumulation in roots, other mechanisms like radial and longitudinal transport are implied in the translocation of U to the shoot.     

Redox reaction of iodine in paddy soil investigated by field observation and the I K-Edge XANES fingerprinting method

In order to elucidate the cause for the leaching of iodine in a flooded paddy field, we investigated the transformation of an iodine species affected by the water management of the paddy field. The increased concentration of iodide (I(-)) in soil solution of a flooded paddy field suggested that I(-) was leached from the soil under anaerobic conditions. The post-edge feature of X-ray absorption near-edge structure (XANES) for iodate (IO(3)(-)) spiked to soil totally disappeared after anaerobic incubation of the soils, and I(-) was dissolved in the solution. On the other hand, I(-) in contact with the soil was not likely to be oxidized to IO(3)(-) under aerobic incubation. Iodine was leached out in soil solution as I(-) under anaerobic conditions, whereas part of the iodine species was retained by soil as I(2) or organoiodine both under anaerobic and aerobic conditions.     

Role of the fungal mycelium in the retention of radiocaesium in forest soils

The aim of this work was to study possible binding of 137Cs to various organic components in the soil and fungi, by using various sequential extraction procedures. The retention and binding of 137Cs has been studied in two horizons Of/Oh and Ah/B of a Ukrainian forest soil. The exchangeable fractions 137Cs from soil (sum of H2O and 1 M NH4OAc fraction) were found to be 12% in the organic-rich layer (range 11-14%) and 23% in the organic-poor (range 20-29%). The hydrolysis with 10% H2SO4 resulted in an additional release of 30% of 137Cs from the organic-rich soil (range 30-35%) and 38% from the organic-poor soil horizon (range 27-53%). Extraction with 30% H2O2 released 11 and 15% of the 137Cs activity from organic-rich and organic-poor soil horizons. The corresponding values for treatment with 98.8% NaOCl were about 27% in both types of soil. About 11% of the total 137Cs activity was found in the humic acid fraction, about 5% in the fulvic fraction and 46% in the residue fraction. Relatively high level of 137Cs activity in soil (ca. 50%) was thus still left unsolved in the residue fraction. About 29% of 137Cs activity concentration in fungal mycelia was found as water soluble with a range of 11 to 41%. Additionally 24% of the 137Cs activity from mycelia was released by 1 M ammonium acetate extraction. Together, water and 1 M ammonium acetate extraction released about 53% of the total 137Cs activity in the mycelia. In fruit bodies of mycorrhizal fungi, 68% of the total 137Cs inventory was found to be water soluble at room temperature and 93% at 80 degrees C.     

Effects of earthworm activity on fertility and heavy metal bioavailability in sewage sludge

The potential for using earthworms (Eisenia fetida) to improve fertility and reduce copper and cadmium availability in sewage sludge was tested by laboratory incubation experiments. Results comparing sewage sludge with and without earthworm treatment showed that earthworm activity decreased the contents of organic matter, total nitrogen, but increased the contents of available nitrogen and phosphorus and had no significant effect on the contents of total phosphorus, total potassium and available potassium. After incubation of the sewage sludge with earthworms for 60 days, the contents of Cu and Cd in the earthworms increased with the increase of additional Cu up to 250 mg kg(-1) and Cd up to 10 mg kg(-1). Bioconcentration factors (BCF) were higher than 1 only for Cd when the addition rate was lower than 5 mg kg(-1), which indicates that the earthworms can only accumulate Cd when the concentration of Cd is low in sewage sludge. Bioavailability of Cd and Cu was evaluated by applying sewage sludge with and without earthworm treatment to soil and then growing cabbage plants. The results showed that earthworm treatment increased the biomass of cabbage and decreased the bioaccumulation of Cd and Cu in the cabbage plants.     

水源地生态补偿标准估算——以贵阳鱼洞峡水库为例

鱼洞河是乌江水系的一个小支流,为下游贵阳市提供饮用水水源。在鱼洞河上下游之间建立生态补偿机制,理论上需要知道上游治理污染和维护生态环境的费用,以及下游对上游提供的生态环境服务的支付意愿。只有下游的支付意愿大于上游的费用,上下游之间的生态补偿机制才有理论可能性。在对上游龙里县汇水区进行实地调研后,重点评估了当地安装沼气系统、坡耕地(≥25°)退耕还林、其他地区的土壤侵蚀防治以及点源污染治理费用,得出上游治理投资费用为199万元,年度费用每年89.2万元-168万元。采用意愿调查法(CVM)对贵阳市自来水用户对上游环境服务的支付意愿进行了评估。采用简单随机抽样方法在贵阳3个区内选取了900户作为样本,结果表明,有62.7%的人愿意为生态补偿付费。采用PROBIT模型,可以计算出为避免鱼洞河水质恶化的支付意愿均值为0.37元/m3,贵阳市自来水用户总的支付意愿每年达847万元。结果表明在鱼洞河水源地进行上下游生态补偿理论上是可能的,补偿标准介于上游费用与下游支付意愿之间。     

The co-application of earthworms (Dendrobaena veneta) and compost to increase hydrocarbon losses from diesel contaminated soils

The feasibility of using composted civic waste for the remediation of a soil contaminated with petroleum hydrocarbons (extractable petroleum hydrocarbons (EPH) 10+/-1.8 g kg(-1) and total 16 USEPA PAH 1.62+/-0.5 g kg(-1)) was assessed. The effects of compost to soil ratio, in combination with and without earthworm presence (Dendrobaena veneta), upon the loss of contaminants were determined for EPH (GC-FID) and PAH (GC-MS), respectively. Increasing the ratio of compost substrate to hydrocarbon impacted soil (1:0.5, 1:1, 1:2 and 1:4 (soil:compost wt/wt)) in the absence of earthworms resulted in significantly (p<0.05) greater losses of both EPH and SigmaPAH after an 84 d incubation period, when compared to the soil only control. Where earthworms were present without compost, EPH losses were significantly (p<0.05) enhanced in the soil only treatment (33.4+/-5.3% residual) compared to the soil only control (54.4+/-5.3% residual). However, PAH loss in the soil only treatment (with-earthworm presence) were only slightly enhanced (65.3+/-9.3% residual), with respect to the soil only control (69.2+/-6.4% residual). Synergistic benefits of both earthworm and compost presence were most significant for PAHs (p<0.05), and less so for EPH. (14)C-respirometer studies, to establish catabolic competence in terms of microbial mineralisation of key hydrocarbons, complemented the hydrocarbon analysis.     

Development of extraction method of pharmaceuticals and their occurrences found in Japanese wastewater treatment plants

In this study, occurrence of 66 PPCPs (pharmaceuticals and personal care products) in liquid and solid phases of sewage sludge was elucidated. The extraction methods for the PPCPs from sludge were newly developed employing Pressurized Liquid Extraction (PLE) and Ultrasonic Solvent Extraction (USE). As an appropriate method, PLE using water (pH2), PLE using methanol (pH4), and USE using mixture of methanol and water (1/9,v/v, pH11) was found most effective because total recovery of most of the PPCPs indicated 40 to 130%. The developed extraction method with previously developed method for liquid phase analysis was applied to field survey at wastewater treatment plants (WWTPs) in Japan. 56 compounds were detected from the primary sludge and 61 compounds were detected from the excess sludge. The concentration was ranged between several ng/g and several μg/g. Solid-water distribution coefficient (Log K_d) ranged between 0.9 L/kg (Caffeine) and 3.7 L/kg (Levofloxacin) for primary sludge and between 1.4 L/kg (Sulpirid) and 4.3 L/kg (Mefenamic acid) for excess sludge.     

Plant induced changes in concentrations of caesium, strontium and uranium in soil solution with reference to major ions and dissolved organic matter

For a better understanding of the soil-to-plant transfer of radionuclides, their behavior in the soil solution should be elucidated, especially at the interface between plant roots and soil particles, where conditions differ greatly from the bulk soil because of plant activity. This study determined the concentration of stable Cs and Sr, and U in the soil solution, under plant growing conditions. The leafy vegetable komatsuna (Brassica rapa L.) was cultivated for 26 days in pots, where the rhizosphere soil was separated from the non-rhizosphere soil by a nylon net screen. The concentrations of Cs and Sr in the rhizosphere soil solution decreased with time, and were controlled by K+NH(4)(+) and Ca, respectively. On the other hand, the concentration of U in the rhizosphere soil solution increased with time, and was related to the changes of DOC; however, this relationship was different between the rhizosphere and non-rhizosphere soil.     

Phytoextraction for clean-up of low-level uranium contaminated soil evaluated

Spills in the nuclear fuel cycle have led to soil contamination with uranium. In case of small contamination just above release levels, low-cost yet sufficiently efficient remedial measures are recommended. This study was executed to test if low-level U contaminated sandy soil from a nuclear fuel processing site could be phytoextracted in order to attain the required release limits. Two soils were tested: a control soil (317 Bq 238U kg(-1)) and the same soil washed with bicarbonate (69 Bq 238U kg(-1)). Ryegrass (Lolium perenne cv. Melvina) and Indian mustard (Brassica juncea cv. Vitasso) were used as test plants. The annual removal of soil activity by the biomass was less than 0.1%. The addition of citric acid (25 mmol kg(-1)) 1 week before the harvest increased U uptake up to 500-fold. With a ryegrass and mustard yield of 15,000 and 10,000 kg ha(-1), respectively, up to 3.5% and 4.6% of the soil activity could be removed annually by the biomass. With a desired activity reduction level of 1.5 and 5 for the bicarbonate-washed and control soil, respectively, it would take 10-50 years to attain the release limit. However, citric acid addition resulted in a decreased dry weight production.     

Bioaccumulation and biological effects in the earthworm Eisenia fetida exposed to natural and depleted uranium

The accumulations of both natural (U) and depleted (DU) uranium in the earthworms (Eisenia fetida) were studied to evaluate corresponding biological effects. Concentrations of metals in the experimental soil ranged from 1.86 to 600 mg kg⁻¹. Five biological endpoints: mortality, animals’ weight increasing, lysosomal membrane stability by measuring the neutral red retention time (the NRRT), histological changes and genetic effects (Comet assay) were used to evaluate biological effects in the earthworms after 7 and 28 days of exposure. No effects have been observed in terms of mortality or weight reduction. Cytotoxic and genetic effects were identified at quite low U concentrations. For some of these endpoints, in particular for genetic effects, the dose (U concentration)-effect relationships have been found to be non-linear. The results have also shown a statistically significant higher level of impact on the earthworms exposed to natural U compared to depleted U.     

千岛湖配水工程的环境成本估算——基于调水区支付意愿调查

由于水资源分布不均、水污染日趋严重,调水工程已不仅用以解决城市资源型缺水,也成为一些地区缓解水质型缺水问题的途径,但是这些耗资巨大的调水工程往往对周围自然生态环境可能产生巨大影响,可能带来的环境成本不容忽视。以千岛湖配水工程为例,通过在调水地进行实地调研和问卷调查,运用Tobit模型分析影响居民支付意愿的因素,基于意愿调查法(CVM)分析了建德市人民对千岛湖配水工程的生态环境影响的支付意愿,并以此估算该工程的环境成本。结果表明,调水地居民对恢复和改善可能破坏的生态环境的平均支付意愿约为每人每年377.6～542.1元,按照年配水量9.78亿 m³可以计算每吨水的环境成本约为0.15～0.21元。由此估算,工程期内千岛湖配水工程可能造成的环境成本总计约为5.80～8.28亿元,高于2014年公布的《杭州市第二水源千岛湖配水工程环境影响报告书》(下文简称《报告书》)中对该工程的环境经济影响评价3.70亿元。千岛湖配水工程的环境成本不容忽视,必须建立科学的生态补偿机制,加强监管;同时受水地也应积极加强污染治理和节约用水,共同解决城市水质型缺水问题。     

Using nematodes in soil ecotoxicology

Nematodes represent a very abundant group of soil organisms and non-parasitic species are important for soil quality and in the soil food web. In recent years, it has been shown that nematodes are appropriate bioindicators of soil condition and they are also suitable organisms for laboratory toxicity testing. The aims of this paper are to overview and critically assess methods and approaches for researching soil nematode ecotoxicology. In natural ecosystems, nematode abundance and community structure analyses were proved to be sensitive indicators of stress caused by soil pollutants and ecological disturbance. Community structure analyses may be approached from a functional or ecological point of view; species are divided into groups according to their feeding habits or alternatively the maturity index is calculated according to their ecological strategy. Many environmental factors have the potential to affect nematode community, which consequently results in high space and time variability. This variance is major handicap in field ecotoxicological studies because pollutant-nematode relationships are obscured. For prospective risk assessment of chemicals, several toxicity tests with nematodes were developed and are increasingly used. Sensitivity of these tests is comparable to tests with other soil species (e.g. enchytraeids, earthworms and springtails) while tests are less demanding to space and time. Most studies have focused on metal toxicity but organic compounds are almost overlooked. Endpoints used in tests were often mortality, reproduction or movement, but more sublethal endpoints such as feeding or biomarkers have been used recently too. Although there is an increasing amount of knowledge in soil nematode ecotoxicology, there is still a lot of various issues in this topic to research.     

邹城东滩矿区复垦土壤微生物量碳与#br# 基础呼吸的特征

探究复垦土壤微生物量碳与基础呼吸的特征及其演变归因,有助于监测复垦土壤质量演变,并为提高复垦土壤质量提供科学依据。利用“空间代替时间”的方法研究了邹城东滩矿区复垦土壤微生物量碳（MBC）与基础呼吸（SBR）随复垦年垦的变化及其与土壤环境因子的关系。结果表明：复垦土壤MBC和微生物熵（qSMBC）随复垦年限呈增加趋势;复垦土壤SBR均显著高于对照,土壤代谢熵（qCO2）随复垦年限趋于降低,复垦后土壤微生物量逐渐恢复,同时土壤微生物对碳源利用效率逐渐提高,说明土壤环境逐渐有利于土壤微生物的生长。土壤MBC与碱解氮、总氮和有机碳呈极显著正相关（p＜0.01）,反映土壤养分缺乏是复垦后土壤微生物生长的主要限制因素。土壤代谢熵（qCO2）与土壤碱解氮、速效磷和MBC均呈极显著负相关（p＜0.01）与pH呈显著正相关（p＜0.05）,说明氮磷等元素的缺乏以及较高的土壤pH环境是限制微生物生长的重要因素。这些对全面监测复垦后土壤质量的演变,并指导今后的复垦工作具有重要理论与实践意义。 关键词： 采煤塌陷区;土壤微生物量碳;土壤微生物熵;基础呼吸     

Beyond contaminated land assessment: On costs and benefits of bioaccessibility prediction

Advances towards sustainable land management necessitate application of a broader portfolio of decision-support tools that improve evaluation of contaminated land. Over the last decade regulators have directed concerted effort towards rationalization of risk-based contaminated land policies recognizing bioavailability and bioaccessibility as concepts to be incorporated into risk assessments. The desire for a precise and rapid method to inform consideration of bioavailability and bioaccessibility to support risk assessment of contaminated land has never been greater. This study presents a comprehensive appraisal of both emerging non-exhaustive extraction techniques (subcritical water extraction and Brij 700 extraction) developed to reflect polycyclic aromatic hydrocarbon (PAH) bioaccessibility to microorganisms as well as formerly demonstrated methodologies (the use of cyclodextrins and butanol extraction). Application of unified evaluation criteria across different techniques enabled comparison not only from the bioaccessibility prediction perspective but also analysis of economical (cost of extraction) and practical (such as extraction time) measures. Whilst the use of cyclodextrins was the best predictor of the bioaccessible fraction for the majority of compounds, other methods appeared more cost- and time-effective. Juxtaposition of the techniques presented in this study assists establishing cost-benefit trade-offs of different non-exhaustive extraction techniques and contributes to tailoring information on contaminant bioaccessibility to support risk evaluation on contaminated sites.