How do long-term development and periodical changes of river-floodplain systems affect the fate of contaminants? Results from European rivers

In many densely populated areas, riverine floodplains have been strongly impacted and degraded by river channelization and flood protection dikes. Floodplains act as buffers for flood water and as filters for nutrients and pollutants carried with river water and sediment from upstream source areas. Based on results of the EU-funded “AquaTerra” project (2004-2009), we analyze changes in the dynamics of European river-floodplain systems over different temporal scales and assess their effects on contaminant behaviour and ecosystem functioning. We find that human-induced changes in the hydrologic regime of rivers have direct and severe consequences on nutrient cycling and contaminant retention in adjacent floodplains. We point out the complex interactions of contaminants with nutrient availability and other physico-chemical characteristics (pH, organic matter) in determining ecotoxicity and habitat quality, and draw conclusions for improved floodplain management.     

Uptake kinetics of metals by the earthworm Eisenia fetida exposed to field-contaminated soils

It is well known that earthworms can accumulate metals. However, most accumulation studies focus on Cd-, Cu-, Pb- or Zn-amended soils, additionally few studies consider accumulation kinetics. Here we model the accumulation kinetics of 18 elements by Eisenia fetida, exposed to 8 metal-contaminated and 2 uncontaminated soils. Tissue metal concentration was determined after 3, 7, 14, 21, 28 and 42 days. Metal elimination rate was important in determining time to reach steady-state tissue metal concentration. Uptake flux to elimination rate ratios showed less variation and lower values for essential than for non-essential metals. In theory kinetic rate constants are dependent only on species and metal. Therefore it should be possible to predict steady-state tissue metal concentrations on the basis of very few measurements using the rate constants. However, our experiments show that it is difficult to extrapolate the accumulation kinetic constants derived using one soil to another.     

Naturally-assisted metal phytoextraction by Brassica carinata: Role ofroot exudates

Due to relatively high chelant dosages and potential environmental risks it is necessary to explore different approaches in the remediation of metal-contaminated soils. The present study focussed on the removal of metals (As, Cd, Cu, Pb and Zn) from a multiple metal-contaminated soil by growing Brassica carinata plants in succession to spontaneous metallicolous populations of Pinus pinaster, Plantago lanceolata and Silene paradoxa. The results showed that the growth of the metallicolous populations increased the extractable metal levels in the soil, which resulted in a higher accumulation of metals in the above-ground parts of B. carinata. Root exudates of the three metallicolous species were analysed to elucidate their possible role in the enhanced metal availability. The presence of metals stimulated the exudation of organic and phenolic acids as well as flavonoids. It was suggested that root exudates played an important role in solubilising metals in soil and in favouring their uptake by roots.     

Preparation of calcium oxalate—bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters

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 × 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. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A field survey—Staroe lake suffering from atmospheric deposition in the region north of the Arctic Circle

Background, aim, and scope  The Arctic holds large stores of minerals, and extracted materials are provided to the world’s economy; in this sense, the Arctic issue associated with mining is not local but global. In a part of the Arctic region (the Kola Peninsula, 66–70° N and 28–41° E), metal levels are generally elevated in the lake sediment. There is a question as to what results in elevated metal levels—a natural process (naturally abundant minerals) or an anthropogenic process (mining and metallurgy). In terms of solving this question, Staroe lake located on the Kola Peninsula was researched as a case study. Materials and methods  The following parameters were determined in relation with Staroe lake: (1) the current quality of the lake’s water—each 1,000-ml sample was collected at a surface point and a deep point (near the bottom layer), and the collected samples were directly analyzed after filtration; (2) atmospheric bulk deposition—bulk deposition was collected using a set of three rainwater samplers near the lake. In addition, bulk deposition was collected in a background site (250 km to the southwest of the smelter complex) as a reference; and (3) sediment profile (plus principal component analysis)—lake-bottom sediment was collected by an open-gravimetric column sampler equipped with an automatic diaphragm. After collection, the sample columns were cut at a 1-cm interval for analysis. Eigenvalues and variances by factor were calculated from the correlation coefficients. Results  The obtained data show that (1) naturally poor elements (Cu, Ni, Si, and SO₄ ²⁻) dominantly influence the lake’s water quality; (2) they are transported from the anthropogenic sources to the study lake through the atmospheric pathway; (3) mainly the contents of Cu, Ni, Sr, and Ca have influenced the sediment quality since the 1950s, corresponding to the industrial movement; and (4) Cu, Ni, and Sr originate from an anthropogenic source (smelter), and Ca originates from both natural and anthropogenic sources. Discussion  As compared with the Russian standard (San Pin 2.1.980–00), the contents of NO₃ ⁻ (50.3 ± 0.1 mg l⁻¹) and particulates (2.3 ± 0.2 mg l⁻¹) exceeded the standard levels (0.7 mg l⁻¹ NO₃ ⁻ and 45 mg l⁻¹ particulates); Staroe lake may be slightly contaminated. However, the contamination factor (comparison with the background data) implies that Staroe lake is considerably contaminated. There is a strong possibility that fine overburden detritus (<0.1 mm diameter) may be transported from an open pit to the study lake by natural forces such as wind. Although it is difficult to suppose that one factor dominantly affects the sediment quality, it follows from a factor analysis that factors 1 and 2 account for about 70% of the total variance: Factor 1 is the most dominant, and factor 2 is the second most dominant in the variability of sediment quality. It is considered that Cu, Sr, and Ni in factor 1 originate from anthropogenic sources because they are poor in sediment rocks. Conclusions  The field survey conducted in Staroe lake can give the following answers to the key objectives: (1) The present water quality is affected by Cu, Ni, Si, and SO₄ ²⁻ in light of the contamination factor, and these elements originate from anthropogenic sources (the smelter and the open pit) and are transported to the lake through the atmospheric pathway; (2) the sediment profile and statistic analysis show that the lake quality has been influenced by deposition of metals since the 1950s; and (3) Cu, Ni, Sr, and Ca have influenced the sediment quality in light of the most dominant factor—Cu, Ni, and Sr originate from an anthropogenic source, whereas Ca comes from both natural and anthropogenic sources. Recommendations and perspectives  The presented lake survey shows that the dispersion of human-related pollutants via the atmospheric pathway takes place in the Arctic region. If the current pollution continues without countermeasures, the high-latitude environment may lose its original characteristics; hence, this subject is important when considering how to implement a wide range of environmental protection measures in the Arctic.     

锦州湾沉积物芯样中重金属污染及变化动态

研究了锦州湾海域底质沉积物中重金属（Zn,Pb,Cd,Fe,Mn）的含量分布,并以一个代表性的水平剖面和一个垂直剖面（J06号芯样）分析了重金属含量变化动态。通过回归计算得出几种金属在水平距离上的变化方程;在分析该湾沉积理化环境基础上,探讨了重金属地球化学相的垂向含量变化,Fe、Mn二元素的垂直剖面的成岩演变。认为沉积物中金属元素释放出来而污染上覆海水,最后得出该湾金属的污染程度及环境现状的结论。     

不同形态P对Cu、Zn、Cd联合生物毒性效应的影响

运用水潘趋光行为的抑制试验研究了水体中不同磷形态和重金属(Cu、Zn、Cd)共同存在时的联合生物毒性效应.结果表明,水体中重金属的生物毒性不仅取决于它们的种类和浓度,也与溶液中共存的P形态有关.重金属对水溞的生物毒性由强至弱依次为Cu2 ＞Zn2 ＞Cd2 ;当溶液中存在不同形态的P时,重金属的生物毒性发生了改变.中等P营养水平(TP为0.05mg·L-1)时,不同形态P的存在可显著降低Cu、Zn、Cd的生物毒性,在某种程度上减轻重金属对生物的伤害.不同形态P对重金属生物毒性的拮抗作用顺序为H2PO-4≈HPO24-＞PO34-.因此,重金属污染与富营养化双重胁迫水体的生物毒性,将可能因水体中P形态的不同而产生差异.     

Environmental application of three-dimensional graphene materials as adsorbents for dyes and heavy metals: Review on ice-templating method and adsorption mechanisms

The remediation of wastewater requires treatment technologies which are robust, efficient, simple to operate and affordable such as adsorption. Lately, three-dimensional (3D) graphene based materials have attracted significant attention as effective adsorbents for wastewater treatment. The intrinsic properties of 3D graphene structure such as large surface area and interconnected porous structure can facilitate the transport of pollutants into the 3D network and provide abundant active sites for trapping the pollutants. For the synthesis of 3D graphene structure, ice-templating is commonly practiced due to its facile steps, cost effectiveness and high scalability potential. This review covers the ice-templating fabrication technique for 3D graphene based materials and their application as adsorbents in eliminating dyes and heavy metals from aqueous media. The assembly mechanisms of the ice-templating fsynthesis are comprehensively discussed. Further discussion on the fundamental principles, critical process parameters and characteristics of ice-templated 3D graphene structures is also included. A thorough review on the mechanisms for batch adsorption of dyes and heavy metals is presented based on the structures and properties of the 3D graphene materials. The review further evaluates the dynamic adsorption in packed columns and the regeneration of 3D graphene based materials.     

氨基酸型螯合树脂的合成及其吸附性能

以三乙烯四胺，环氧氯丙烷和氯乙酸为原料，合成了氨基酸结构的螯合树脂，并研究了Ｃｕ＾２＋，Ｐｂ＾２＋，Ｎｉ＾２＋，Ｚｎ＾２＋的吸附性能。结果表明，该树脂对Ｃｕ＾２＋，Ｐｂ＾２＋，Ｐｂ＾２＋，Ｎｉ＾２＋比对Ｚｎ＾２＋具有良好的吸附性能，其吸附量可达１．４０，，１．３９，１．２０及０．４ｍｏｌ／ｇ。     

沱江流域水系沉积物重金属的潜在生态风险评价

通过对沱江流域水系沉积物的系统研究,查明了重金属元素含量的空间分布特征,进行了潜在生态风险质量评价。研究结果显示,在两支流交汇之前,沉积物中重金属的污染水平从上游到下游呈上升趋势,矿业活动是水环境中重金属的主要来源,两支流交汇之后元素含量有较明显升高,显示两河汇流叠加对沱江下游水系沉积物有较大的影响;与前人研究相比,各元素含量有较明显的增加;沱江水系沉积物中重金属的潜在生态风险水平较低,大多属于轻微生态风险,Cd的潜在生态危害程度最严重;多种重金属的潜在生态风险指数(R1)表明河流重金属污染属于轻微生态危害,其受危害程度由大到小的顺序为:沱江>石亭江>绵远河。