Valérie Cappuyns

Solid phase speciation of arsenic by sequential extraction in standard reference materials and industrially contaminated soil samples

Availability, mobility, (phyto)toxicity and potential risk of contaminants is strongly affected by the manner of appearance of elements, the so-called speciation. Operational fractionation methods like sequential extractions have been applied for a long time to determine the solid phase speciation of heavy metals since direct determination of specific chemical compounds can not always be easily achieved. The three-step sequential extraction scheme recommended by the BCR and two extraction schemes based on the phosphorus-like protocol proposed by Manful (1992, Occurrence and Ecochemical Behaviours of Arsenic in a Goldsmelter Impacted Area in Ghana, PhD dissertation, at the RUG) were applied to four standard reference materials (SRM) and to a batch of samples from industrially contaminated sites, heavily contaminated with arsenic and heavy metals. The SRM 2710 (Montana soil) was found to be the most useful reference material for metal (Mn, Cu, Zn, As, Cd and Pb) fractionation using the BCR sequential extraction procedure. Two sequential extraction schemes were developed and compared for arsenic with the aim to establish a better fractionation and recovery rate than the BCR-scheme for this element in the SRM samples. The major part of arsenic was released from the heavily contaminated samples after NaOH-extraction. Inferior extraction variability and recovery in the heavily contaminated samples compared to SRMs could be mainly contributed to subsample heterogeneity.

Chemical associations of heavy metals and metalloids in contaminated soils near former ore treatment plants: a differentiated approach with emphasis on pHstat-leaching

Application of pHstat-experiments on soil samples of two heavily contaminated sites in northern Belgium (Flanders) was used to make long-term risk predictions of environmentally relevant heavy metals (Pb, Cu, Ni, Zn, Cr) and arsenic. Implementation of the results of other techniques (sequential extractions and mineralogical research) and geochemical modeling with MINTEQA2 was used to obtain a refined understanding of the geochemical association and the processes that control pH-dependent leaching characteristics of the contaminants. The soil on the first site (a former arsenic refinery in Reppel) was extremely polluted with As, Cu (percentage level), Co and Ni (>0.5%) and leaching of contaminants, which is already alarming, will further increase in the near future by soil acidification. The second site was contaminated with so-called burnt pyrite (sulfuric acid industry) containing high concentrations of Pb, Cu, As and Zn (>0.1%) and a serious threat of metal leaching will manifest if no measures are taken. The kinetics of buffering reactions were evaluated by mathematically fitting of the titration curves. Thereby, two independent proton buffer reactions (rapid and slow) were differentiated and quantified. In the paper, some aspects of the pHstat-procedure were also reconsidered and evaluated. It was shown that one of the critical parameters, namely the duration of the leaching, needs to be extended to 96 h. A 24-h test was observed to be inadequate in assessing heavy metal release properly.

From geochemical background determination to pollution assessment of heavy metals in sediments and soils

Establishing geochemical background concentrations to distinguish the natural background from anthropogenic concentrations of heavy metals in sediments and soils is necessary to develop guidelines for environmental legislation. Due to the fact that the background concentrations strongly depend on geological characteristics such as mineral composition, grain size distribution and organic matter content, several normalization methods have been developed. Empirical (geochemical), theoretical (statistical) and integrated methods (combining both empirical and theoretical methods) are the main approaches described in literature for determination of geochemical background concentrations. In this review paper, the different approaches as well as the main normalization methods for heavy metal concentrations in sediments and soils will be discussed. Both geochemical background concentrations and added risk level (maximum permissible addition) should be taken into account for setting up legal threshold limits. Moreover, different approaches to evaluate the pollution status of heavy metals in sediments and soils, from Sediment/Soil Quality Guidelines to quantitative indices (Geo-accumulation Index-Igeo, Enrichment Factor-EF, Pollution Load Index-PLI and Risk assessment Code-RAC) will be presented. Although guidelines to establish whether a sediment or soil is polluted or not are generally only related to total metal concentrations, the available/reactive pool i.e., availability/reactivity of metals should be taken into account for sediment/soil pollution assessment.

Arsenic pollution at the industrial site of Reppel-Bocholt (north Belgium)

An industrial site, polluted with As and heavy metals, was investigated by combining chemical (sequential extractions and pHstat leaching tests), physical and mineralogical characterization of soil samples and slag fragments, and by the analysis of soil porewater aimed at assessing the distribution, speciation and mobility of heavy metals and As. On the site itself, arsenic concentrations up to 3.6% in surficial soil samples and up to 22% in slag fragments were found, together with elevated concentrations (percentage level) of Cu, Co, Ni, Zn and Pb. High concentrations of arsenic (up to 38,000 microg/l) and heavy metals (up to 1700 microg/l Cu and 4700 microg/l Zn) were also found in the in situ sampled soil porewater, highlighting the considerable availability of As, Zn and Cu for uptake by plants and leaching to the ground water. Sequential extractions also indicated a high availability of arsenic and copper in most samples and slag fragments of the industrial site, although poorly reactive phases were encountered as well. pHstat leaching tests confirmed that the present leaching of contaminants is alarming. Moreover, soil acidification will enhance the leaching of contaminants, emphasizing that remediation of the industrial site is urgent. Small scale variability of total metal concentrations and metal speciation, both in the horizontal and vertical direction, and the occurrence of a camouflage layer underline the importance of elaborate sampling for pollution assessment on an industrial site.

Potential release of selected trace elements (As, Cd, Cu, Mn, Pb and Zn) from sediments in Cam River-mouth (Vietnam) under influence of pH and oxidation.

Since contaminated river-bed sediments in the Cam River-mouth (Vietnam) are regularly dredged and disposed on land, an understanding of the influence of time, pH and oxidation on the leaching behavior of heavy metals (Cd, Cu, Mn, Pb and Zn) and arsenic is necessary for the management of these dredged materials. A 96 h pH(stat)-leaching test to examine the leaching behavior of elements at pre-set pH values (2, 4, 6, 8 (natural), 9 and 11) and a BCR 3-step extraction to clarify the element fractionation, were performed on a freshly-collected wet suboxic sediment and a dry oxidized sediment. All heavy metals and arsenic display a V-shaped pH-dependent leaching pattern with important releases at pHs 2 and 11. At the investigated pH values, the release of As, Mn, Pb and Zn from the oxidized sediment is slower and lower if compared with the suboxic sediment while the opposite trend is found for Cd and Cu at pHs 2-8. The transfer from the acid-soluble (exchangeable and carbonate-bound) fraction to the reducible (Fe and Mn hydr/oxide-bound) fraction is consistent with the lower leachability of As, Mn and Zn at pHs 2-8 and Pb at pHs 4-8 after oxidation, while the transfer from the oxidizable (organic matter and sulfide-bound) fraction to the reducible fraction relates to the higher leachability of Cd and Cu at pHs 2-8. The lower leachability of all elements at alkaline pHs 9-11 is due to lower leached concentration of organic matter from the oxidized sediment. Sulfides only play a minor role in controlling the leachability of heavy metals and arsenic.

Integration of sustainable development in higher education's curricula of applied economics: Large-scale assessments, integration strategies and barriers

The attention for sustainable development (SD) is ever growing (Van Poeck, Vandenabeele, & Bruyninckx, 2009). Although the importance of SD integration in higher education (HE), both on strategic and operational level, is often stressed, actual measurements of this integration are less frequent. Therefore, a large scale assessment was set up to assess SD integration within 33 professionally and academically oriented programs of applied economics in a total of 22 Flemish HE institutions. The integration of SD in applied economics programs is crucial for society, among others because business students are our future managers (Ceulemans & De Prins, 2010). The interrelations between different SD integration strategies and the barriers to them were also studied in this research, leading us to a new concept, where two different dimensions of SD integration are combined. From the research we can conclude that an SD integration approach that combines horizontal and vertical integration with bottom-up and top-down seems to be the most beneficial for sustained SD integration efforts.

Strategic selection of an optimal sorbent mixture for in-situ remediation of heavy metal contaminated sediments: Framework and case study

Aquatic sediments contaminated with heavy metals originating from mining and metallurgical activities pose significant risk to the environment and human health. These sediments not only act as a sink for heavy metals, but can also constitute a secondary source of heavy metal contamination. A variety of sorbent materials has demonstrated the potential to immobilize heavy metals. However, the complexity of multi-element contamination makes choosing the appropriate sorbent mixture and application dosage highly challenging. In this paper, a strategic framework is designed to systematically address the development of an in-situ sediment remediation solution through Assessment, Feasibility and Performance studies. The decision making tools and the experimental procedures needed to identify optimum sorbent mixtures are detailed. Particular emphasis is given to the utilization and combination of commercially available and waste-derived sorbents to enhance the sustainability of the solution. A specific case study for a contaminated sediment site in Northern Belgium with high levels of As, Cd, Pb and Zn originating from historical non-ferrous smelting is presented. The proposed framework is utilized to achieve the required remediation targets and to meet the imposed regulations on material application in natural environments.

Occurrence of Vanadium in Belgian and European Alluvial Soils

Vanadium (V) is a naturally occurring trace element, but total concentrations in soils and sediments are also dependent on the parent material and might be influenced by anthropogenic activities (e.g., steel industry). Despite the fact that threshold values for V in soils and/or sediments exist in various European countries, in Belgium, V is not taken into account when the environmental quality of soils and sediments has to be evaluated, despite the existence of several (diffuse) sources for V. In the first part of the study, the occurrence of V alluvial soils in Belgium was compared with V concentrations in alluvial soils (floodplain soils) across Europe. By analysis of both the Belgian and European data, the relationship between physicochemical soil characteristics and total V concentrations was quantified and some areas polluted with V were detected. A regression equation, in which V concentrations in alluvial soils were expressed as a function of major element composition, was proposed for the Belgian and European data. Additionally, single extractions with CaCl2 (0.01 mol L-1) and ammonium-EDTA (0.05 mol L-1) were used to estimate short- and long-term mobility of V in the alluvial soils.

Acid extractable metal concentrations in solid matrices: a comparison and evaluation of operationally defined extraction procedures and leaching tests

Different frequently used methods to determine the influence of acid conditions on heavy metal release from soils, sediments and waste materials, namely pH(stat) leaching tests and acid extractions with acetic acid (HOAc) (0.11 M and 0.43 M) and sodium acetate (NaOAc) (1 M) were compared for 30 samples (soils, sediments and waste materials) with different physico-chemical properties and a different degree of contamination. However, no distinct relationship was found between physico-chemical sample characteristics, total element concentrations and acid-extractable metal concentrations in the presented dataset. pH played an important role in explaining the release of metals from the contaminated soils, sediments and waste materials. The pH-shift after extraction with the different acetic acid solutions (0.11 M and 0.43 M) was both explained by the initial pH of the sample and its acid neutralizing capacity. The pH of the NaOAc extract was well buffered and the release of elements from solid matrices by NaOAc was both the result of the complexation with acetate and pH (pH 5). Generally, a linear correlation was found between the amount of Zn and Cd extracted by 0.11 M HOAc, 0.43 M HOAc and 1 M NaOAc. The amounts of Zn and Cd extracted with HOAc (0.11 M and 0.43 M) were comparable with amounts of respectively Zn and Cd released during pH(stat) leaching at pH 4. However, for Cu, Pb and As, it was often not possible to relate the results of a pH(stat) leaching test to the results of single extractions with acetic acid solutions.

Evaluation of the environmental impact of Brownfield remediation options: comparison of two life cycle assessment-based evaluation tools

The choice between different options for the remediation of a contaminated site traditionally relies on economical, technical and regulatory criteria without consideration of the environmental impact of the soil remediation process itself. In the present study, the environmental impact assessment of two potential soil remediation techniques (excavation and off-site cleaning and in situ steam extraction) was performed using two life cycle assessment (LCA)-based evaluation tools, namely the REC (risk reduction, environmental merit and cost) method and the ReCiPe method. The comparison and evaluation of the different tools used to estimate the environmental impact of Brownfield remediation was based on a case study which consisted of the remediation of a former oil and fat processing plant. For the environmental impact assessment, both the REC and ReCiPe methods result in a single score for the environmental impact of the soil remediation process and allow the same conclusion to be drawn: excavation and off-site cleaning has a more pronounced environmental impact than in situ soil remediation by means of steam extraction. The ReCiPe method takes into account more impact categories, but is also more complex to work with and needs more input data. Within the routine evaluation of soil remediation alternatives, a detailed LCA evaluation will often be too time consuming and costly and the estimation of the environmental impact with the REC method will in most cases be sufficient. The case study worked out in this paper wants to provide a basis for a more sounded selection of soil remediation technologies based on a more detailed assessment of the secondary impact of soil remediation.