Monitoring of subaqueous depots with active barrier systems for contaminated dredged material using dialysis samplers and DGT probes

Background, Aims and Scope  Disposal of dredged material in subaqueous depots is increasingly considered an economic and ecologically sound option in managing contaminated dredged material. The concept of subaqueous disposals capped with active barrier systems has been developed to minimize this risk of contaminant release. As such a depot represents a permanent installation within a sensitive ecosystem, it requires a thorough monitoring concept. It is the goal of this work to develop such a concept regarding general considerations and results of laboratory and field investigations. Methods  In addition to the state-of-the-art techniques developed for other under-water constructions, this monitoring concept is developed with particular respect to the chemical isolation of the dredged material from the overlying water body. It comprises the use of seepage meters, dialysis samplers, and DGT gel probes for determining the migration of selected target solutes. The capability of the dialysis samplers is demonstrated by comparing field results with model calculations. The appropriateness of DGT probes to assess the impact of humic substances on trace metal speciation and on copper toxicity is demonstrated with the aid of laboratory experiments. Results and Discussion  The experimental results show that, by using dialysis samplers, the temporal changes in concentration-depth-profiles of heavy metals in the pore solution can be monitored. Additionally, the application of DGT probes facilitates the in situ detection of labile species of a metal in the presence of dissolved humic substances, which serves to reflect its toxicity. Conclusions. Three subsequent monitoring phases are distinguished on the basis of both general considerations and the findings from field results: A hydraulic phase that is characterized by compaction and pore water expulsion, a geochemical phase in which the demobilization of pollutants can occur due to substantial changes in the physico-chemical conditions (pH, EH), and a steady-state-phase where pore water flow and geochemical conditions are approaching their minimum. Recommendations and Outlook  The monitoring concept suggested here provides a versatile tool to assess the chemical isolation of subaqueous sediment depots and other contaminated sediment sites. This is of great importance as subaqueous disposal is increasingly considered a future management strategy as space for upland disposal is limited and treatment, in general, proves to be too costly.     

氧化节杆菌生物降解苯并芘

A pot experiment was conducted with multi-metal (Pb, Cd, Cu, and Zn) contaminated acidic soil to investigate changes in available metal burden resulting from the application of industrial wastes (fly ash and steel slag). The efficiency of amendments-induced metal stabilization was evaluated by diffusive gradients in thin films (DGT), sequential extraction, and plant uptake. The stability of remediation was assessed by an acidification test and by chemical equilibrium modeling. Addition of fly ash (20 g kg-1 ) and steel slag (3 g kg-1 ) resulted in similar increase in soil pH. Both amendments significantly decreased the concentrations of metals measured with DGT (C DGT) and the metal uptake by Oryza sativa L. Significant correlations were found between C DGT and the concentration of a combination of metal fractions (exchangeable, bound to carbonates, and bound to Fe/Mn oxides), unraveling the labile species that participate in the flux of metal resupply. The capability of metal resupply, as reflected by the R (ratio of C DGT to pore water metal concentration) values, significantly decreased in the amended soils. The C DGT correlated well with the plant uptake, suggesting that DGT is a good indicator for bioavailability. Acidification raised the extractable metal concentration in amended soil but the concentration did not return to the pre-amendment level. Equilibrium modeling indicated that the soil amendments induced the precipitation of several Fe, Al and Ca minerals, which may play a positive role in metal stabilization. Chemical stabilization with alkaline amendments could be an effective and stable soil remediation strategy for attenuating metal bioavailability and reducing plant metal uptake.     

华中地区水旱轮作酸性土磷、铁形态转化及机理

为探讨华中地区水旱轮作体系酸性土壤磷与铁的形态转化以及磷生物有效性变化,本研究于2018年和2019年水稻收获后采集该区域典型酸性红壤（低磷铁比）和黄棕壤（高磷铁比）,采用张守敬-杰克逊无机磷分级方法和梯度扩散薄膜（DGT）技术,对干湿交替培养样品磷形态、生物有效性磷（DGT-P）与铁（DGT-Fe）、Fe（Ⅱ）及无定形氧化铁（Fe_ox）等进行定量分析。结果表明：淹水过程中黄棕壤和红壤pH逐渐升高趋于中性;二者氧化还原电势（Eh）在淹水期间降低,土壤环境呈明显的还原条件。淹水过程黄棕壤和红壤中Fe²⁺与Fe_ox均增加,干燥后均明显降低。黄棕壤与红壤磷形态以铁结合态磷（Fe-P）与闭蓄态磷（Oc-P）为主,干湿交替过程中黄棕壤Oc-P向Fe-P转化,红壤Fe-P向Oc-P转化。在水-土界面以下120 mm土壤垂直剖面内,黄棕壤DGT-P和DGT-Fe释放水平先增加后减少;红壤DGT-Fe增加,DGT-P减少,黄棕壤P和Fe的同步释放相关性更显著。研究表明,干湿交替条件下酸性土壤磷形态主要是Fe-P与Oc-P之间转化,低P/Fe红壤以磷闭蓄化为主,高P/Fe黄棕壤Fe-P增加,以铁吸附磷为主;淹水导致DGT-P含量增加,生物有效性增加;干燥过程磷闭蓄化加深,但磷有效性并无明显降低,这与土壤磷水平有关。     

太湖梅梁湾沉积物中的重金属生物可利用性及生态风险评价

[目的]研究太湖梅梁湾沉积物中重金属的污染状况和生态风险。[方法]对重金属总量和生物有效浓度进行了分析,采用发光细菌法进行了沉积物毒性研究,并对重金属环境风险进行了评价。[结果]梅梁湾沉积物中Cr处于无污染状态,Zn、Cu、Pb和Ni属于轻度污染水平。DGT测定的有效态浓度和释放通量结果表明,Ni、Zn和Cu的生物可利用性高于Cd和Pb。发光细菌毒性测试和Hakanson潜在生态风险指数评价也表明,梅梁湾沉积物不具有生物毒性,属于低生态风险。[结论]需对梅梁湾沉积物中的Ni污染进行控制。     

长期磷肥不均投入下黄土高原土壤磷素有效性及与土壤性质关系分析

由于科学施肥指导工作和生产实际的脱节,过量施用磷肥的现象普遍存在,进而造成大量磷素在土壤中累积。准确评价土壤中磷素的有效性是土壤磷素科学管理的基础。国际上梯度扩散薄膜技术(DGT)和传统方法相比可以更为准确地反映土壤中元素的生物有效性。以黄土高原具有代表性的60个土壤样品为研究对象,采用传统Olsen法和DGT技术评价多年磷肥投入不均条件下黄土高原地区土壤磷储量及其有效性现状,研究了DGT技术测定的DGT-P与全磷、Olsen-P之间的关系,并利用通径分析探究了土壤磷素有效性和土壤相关理化指标之间的关系。结果表明:黄土高原地区土壤磷素分布不均匀,缺磷与富磷现象并存,富磷土壤主要是耕地样品。磷素活化系数(Olsen-PAC)小于2.0%的土壤样品占76.67%,绝大部分土壤样品磷素有效性低。耕地磷肥投入量过高,活化土壤中的无效磷是黄土高原地区磷素科学管理的主要目标。土壤DGT-P与全磷、Olsen-P呈显著相关性(P0.01)。黏粒对土壤磷素有效性的直接影响最大,对Olsen-PAC的影响为正效应,对DGT法测定的磷素活化系数(DGT-PAC)的影响为负效应。土壤黏粒含量越高,有效磷库越大,土壤中供植物吸收利用的磷反而越少。     

基于DGT技术分析土壤重金属Cd、Ni的老化特征

为明确重金属在土壤中的老化进程,锁定关键影响因子,采用梯度扩散薄膜(DGT)技术探究了外源添加Cd和Ni两种重金属在6种不同类型土壤中的老化特性,并探讨了影响重金属老化过程的关键因子。结果表明:Cd、Ni在不同土壤中的老化过程差异性明显,Ni比Cd更易老化。进入土壤中的重金属老化过程大致分为3个阶段,添加后20～30 d为快速老化阶段,30～60 d为缓慢老化期,除个别高污染土壤外,其余土壤均在60 d后基本达到平衡。数据分析结果表明,6种土壤中Cd、Ni的老化平衡浓度由初始浓度决定,初始浓度、CEC等因子为影响Cd、Ni老化速率的主控因素。DGT作为一种原位、非破坏性、不引入外源离子的监测技术,可以动态展示土壤外源添加重金属在老化过程中的活性变化,对评估土壤重金属污染风险具有重要参考价值。     

梯度扩散薄膜技术在干旱区土壤中原位测定磷素的方法及其应用

薄膜扩散梯度技术（diffusive gradients in thin films technique,DGT）是近年来广泛应用于水体、沉积物和土壤中有效态元素生物有效性研究的一种新技术,为确定测定土壤磷素生物有效性的DGT最佳测试条件以及肥料磷在土壤中迁移特性,采用盆栽试验,分析了土壤与DGT作用时间、环境温度、土壤相对含水量对DGT测定的磷素生物有效性影响,并利用DGT测定肥料磷在表面撒施和滴施（4种土壤类型：潮土、灌淤土、灰漠土和草甸土）方式下土壤剖面的迁移规律。结果表明：DGT-P随土壤与DGT作用时间（0-24 h）的增加而增加,在24 h后趋于稳定;DGT-P随土壤相对含水量（20%-100%）的增加而增加,在含水量为80%-100%时最大,当相对含水量增加到120%时,DGT-P则降低;DGT-P随环境温度的增加而增加,在25℃后趋于稳定。与表面撒施处理相比,滴施可以增加5-15 cm肥料磷的分布。而滴施处理的磷的移动性也受到土壤类型和质地的影响,在草甸土（71%砂粒）上运移性较大,在潮土（46.65%砂粒）上运移性较小。总之,DGT测定的土壤磷素生物有效性最佳测试条件为土壤与DGT作用时间在24 h,土壤相对含水量为80%-100%,环境温度25℃,磷肥滴施优于表面撒施,滴施的磷肥能够迁移到更深的土层。     

薄膜扩散梯度(DGT)——技术进展及展望

近年来,薄膜扩散梯度(DGT)技术取得快速的发展,成为最常用的被动采样技术之一。本文详细阐述了DGT在技术方面的研究进展,包括DGT装置构型、固定相和扩散相材料发展、环境样品的前处理与DGT装置放置、DGT样品处理与测定等,针对该技术前期发展存在的不足,提供了有利于DGT操作和功能提升的系统解决方案,同时对未来的发展进行了展望。     

Changes in tolerance of soil microbial communities in Zn and Cd contaminated soils

Trace metals are present in the soil matrix in different forms, and this obscures the relationship between the amounts of metals, their biological availability and effects. Chemical methods have been devised to directly measure the biological available pools of trace metals, but such methods need to be validated against measured exposure of organisms in the soil. We studied acquired Zn- and Cd tolerance of the soil microbial community as a reporter of its exposure, and compared it with chemical determination of Zn and Cd in 10 soils differing in pH, organic matter content, texture, vegetation-/cultivation history and metal contamination. The tolerance was measured as LC₅₀ (i.e. the metal concentration which inhibits 50% of the activity) in suspensions of extracted soil bacteria, by measuring the incorporation rate of [³H] thymidine at different metal concentrations. Chemical determination of Cd and Zn in soils included total concentrations by aqua regia extractions (AR), and total concentrations in extracted pore water (PW). In addition was the ‘effective concentration’ (C_E) determined using the Diffusion Gradients in Thins films method (DGT). The LC₅₀ values correlated better with PW (r²=0.90 for Cd and r²=0.97 for Zn) and C_E (0.90 for Cd and 0.98 for Zn) compared to the correlation with AR (0.72 for Cd and 0.82 for Zn). After excluding a single extremely contaminated soil from the analysis, the correlation of LC₅₀ with AR was much poorer (r²=0.03 (ns) for Cd and r²=0.48 for Zn), whereas correlations remained significant for both PW (0.90 for Cd and 0.87 for Zn) and C_E (0.54 for Cd and 0.84 for Zn). In conclusion, PW fraction of Cd and Zn appear to be the best predictor of trace metal exposure of the soil microorganisms.     

Changes in Cd and Cr fluxes during the bioremediation of phenanthrene

Abstract. Different types of contaminants such as polycyclic aromatic hydrocarbons (PAHs) and metals coexist in different chemical forms in soil. Although bioremediation of organics has been widely studied, little attention has been paid to changes in metal behaviour during the bioremediation process. In this study, the diffusion gradient in thin-film (DGT) technique was used to assess changes in potentially bioavailable Cd and Cr fluxes in soil during the bioremediation of phenanthrene. Fluxes of Cd were low (< 0.2pgcm⁻² s⁻¹) and increased to 0.4–0.9 pg cm⁻² s⁻¹, while Cr(III) fluxes showed an approximately tenfold increase. Results showed that there was increased mobilization of metals associated with the fungal reduction of phenanthrene concentrations by Penicillium frequentans.