Assessment of industrial by-products as amendments to stabilize antimony mine wastes.

The spread of antimony from mine wastes to the environment represents a matter of great concern due to its adverse effects on impacted ecosystems. There is an urgent need for developing and adopting sustainable and inexpensive measures to deal with this type of wastes. In this study the Sb leaching behavior of mine waste rocks and mine tailings derived from the exploitation of Sb ore deposits was characterized using standard batch leaching tests (TCLP and EN-12457-4) and column leaching essays. Accordingly, these mine wastes were characterized as toxic (>0.6 mg Sb L-1) and not acceptable at hazardous waste landfills (>5 mg Sb kg-1), showing also an ongoing Sb release under prolonged leaching conditions. Two industrial by-products were evaluated as amendments to stabilize them, namely deferrisation sludge (DFS) and a by-product derived from the treatment of aluminum salt slags (BP-Al). Mine wastes were amended with different doses (0-25%) of DFS or BP-Al and the performance of these treatments was evaluated employing also batch and column leaching procedures. The effectiveness of DFS to immobilize Sb was much higher than that exhibited by BP-Al. Thus, treatments with 25% BP-Al showed Sb immobilization levels of approximately 33-53%, whereas treatments with 5 and 25% DFS already attained Sb immobilization levels up to approximately 80-90 and 90-99%, respectively. Mine tailings amended with 5% DFS and mine waste rocks amended with 25% DFS decreased their leachable Sb contents below the limit for non-hazardous waste landfill acceptance (<0.7 mg Sb kg-1). Likewise, these DFS treatments were able to revert their toxic characterization. Moreover, the 25% DFS treatment showed to be a long-lasting stabilizing system, efficient at least during a leaching period equivalent to 10-year rainfall with a great Sb leaching reduction (close to 98%). After this long-term leaching process, DFS-treated mine wastes kept their non-hazardous and non-toxic characterization. The amorphous Fe (oxyhydr)oxides composing DFS were responsible for the important Sb removal capacity showed by this by-product. Thus, when DFS was applied to mine wastes mobile Sb was importantly fixed as non-desorbable Sb, showing also a considerable Sb removal capacity in presence of strong competing anions such as phosphate. The application of DFS as amendment presents a great potential to be used as a sustainable long-term stabilizing system of Sb mine wastes.

Application of different alkaline materials as polluted soil amendments: A comparative assessment of their impact on trace element mobility and microbial functions.

Treatment with chemical amendments is among the best techniques to remediate soils highly polluted with trace elements. The use of waste-derived products has several advantages in this regard, mainly in terms of reducing process costs and conserving natural resources. In this study, the performance of the synthetic zeolite NaP1 derived from coal combustion fly ash (SZ) and the by-product generated from the processing of aluminum salt slags (BP) was evaluated with this aim in comparison to calcite (CC). For this purpose, mine soils polluted with Zn, Cd, and Pb were amended under controlled laboratory conditions with different doses (0%, 1%, 2%, 5%, and 10%) of SZ, BP, or CC, and their impact on trace element mobility and microbial functions was evaluated. Specifically, the mobile and mobilizable trace element pools, basal soil respiration, and different enzyme activities were analyzed. Both SZ and BP performed better than CC in the immobilization of trace elements, reaching, respectively, mobility decreases up to 89-94% and 66-87% when applied at a dose of 10%. These amendments reduced the mobile trace element pool by precipitating them as acid-soluble precipitates and/or retaining them in the reducible fraction of soils. The alkaline nature of these materials and the concomitant increase in soil pH caused by their application mainly accounted for this behavior. Additionally, soil microbial functionality improved after amendment, especially in the case of SZ, as shown by dehydrogenase and alkaline phosphatase activities, which significantly increased (p < 0.05) up to 536% and 48%, respectively. Therefore, applying SZ or BP as soil amendments can significantly decrease the mobile trace element contents of heavily polluted soils without negatively affecting soil quality, thus facilitating plant growth to revegetate and reclaim degraded spaces.

Arsenic distribution in a pasture area impacted by past mining activities.

Former mine exploitations entail a serious threat to surrounding ecosystems as after closure of mining activities their unmanaged wastes can be a continuous source of toxic trace elements. Quite often these mine sites are found within agricultural farming areas, involving serious hazards as regards product (feed/food) quality. In this work a grazing land impacted by the abandoned mine exploitation of an arsenical deposit was studied so as to evaluate the fate of arsenic (As) and other trace elements and the potential risks involved. With this aim, profile soil samples (0-50cm) and pasture plant species (Agrostis truncatula, Holcus annus and Leontodon longirostris) were collected at different distances (0-100m) from the mine waste dump and analyzed for their trace element content and distribution. Likewise, plant trace element accumulation from impacted grazing soils and plant trace element translocation were assessed. The exposure of livestock grazing animals to As was also evaluated, establishing its acceptability regarding food safety and animal health. International soil guideline values for As in grazing land soils (50mgkg-1) resulted greatly exceeded (up to about 20-fold) in the studied mining-affected soils. Moreover, As showed a high mobilization potential under circumstances such as phosphate application or establishment of reducing conditions. Arsenic exhibited relatively high translocation factor (TF) values (up to 0.32-0.89) in pasture plant species, reaching unsafe concentrations in their above-ground tissues (up to 32.9, 16.9 and 9.0mgkg-1 in Agrostis truncatula, Leontodon longirostris and Holcus annus, respectively). Such concentrations represent an elevated risk of As transfer to the high trophic-chain levels as established by international legislation. The limited fraction of arsenite found in plant roots should play an important role in the relatively high As root-to-shoot translocation shown by these plant species. Both soil ingestion and pasture intake resulted important entrance pathways of As into livestock animals, showing quite close contribution levels. The cow acceptable daily intake (ADI) of As regarding food safety was surpassed in some locations of the study area when the species Agrostis truncatula was considered as the only pasture feed. Restrictions in the grazing use of lands with considerable As contents where this plant was the predominant pasture species should be established in order to preserve food quality. Therefore, the exposure of livestock animals to As via both soil ingestion and pasture consumption should be taken into account to establish the suitability of mining-impacted areas for gazing.

A comparative study on the influence of different organic amendments on trace element mobility and microbial functionality of a polluted mine soil.

A mine soil heavily polluted with zinc and cadmium was employed to evaluate the capacity of organic amendments of different origin to simultaneously reduce soil trace element mobility and enhance soil microbial functionality. With this aim, four organic products, namely olive processing solid waste (OPSW), municipal solid waste compost (MSWC), leonardite and peat, were applied individually at different doses (0, 1, 2 and 5%) to mine soil under controlled laboratory conditions. Extraction studies and analysis of soil microbiological parameters (basal soil respiration and dehydrogenase, ß-glucosidase, urease, arylsulfatase and acid and alkaline phosphatase activities) were performed to assess the effect of such amendments on soil restoration. Their ability to decrease mine soil mobile trace element contents followed the sequence MSWC > OPSW > peat > leonardite, with the former achieving reduction levels of 78 and 73% for Zn and Cd, respectively, when applied at a dose of 5%. This amendment also showed a good performance to restore soil microbial functionality. Thus, basal soil respiration and dehydrogenase, urease and alkaline phosphatase activities experienced increases of 187, 79, 42 and 26%, respectively, when mine soil was treated with 5% MSWC. Among tested organic products, MSWC proved to be the best amendment to perform both the chemical and the microbial soil remediation.

Antimony distribution and mobility in different types of waste derived from the exploitation of stibnite ore deposits.

Wastes derived from the exploitation of stibnite ore deposits were studied to determine their mineralogical, chemical, and environmental characteristics and establish the Sb distribution and the current and long-term risks of Sb mobilization. Representative samples of mine waste rocks, mine tailings, and smelting waste were studied by X-ray powder diffraction, polarized light microscopy, electron microprobe analysis, and digestion, leaching, and extraction procedures. The main Sb-bearing minerals and phases identified in the smelting waste were natrojarosite, iron (oxyhydr)oxides, mixtures of iron and antimony (oxyhydr)oxides, and tripuhyite; those in the mine tailings and mine waste rocks were iron (oxyhydr)oxides and/or mixtures of iron and antimony (oxyhydr)oxides. Iron (oxyhydr)oxides and natrojarosite had high Sb contents, with maximum values of 16.51 and 9.63 wt% Sb2O5, respectively. All three types of waste were characterized as toxic; the mine waste rocks and mine tailings would require pretreatment to decrease their leachable Sb content before they would be acceptable at hazardous waste landfills. Relatively little of the Sb was in desorbable forms, which accounted for <0.01 and <0.8% of the total Sb content in the smelting waste and mine waste rocks/mine tailings, respectively. Under reducing conditions, further Sb mobilization from mine waste rocks and mine tailings could occur (up to 4.6 and 3.3% of the total content, respectively), considerably increasing the risk that Sb will be introduced into the surroundings. Although the smelting waste had the highest total Sb content, it showed the lowest risk of Sb release under different environmental conditions. The significant Fe levels in the smelting waste facilitated the formation of various Fe compounds that greatly decreased the Sb mobilization from these wastes.

In vivo genetic engineering of murine pancreatic beta cells mediated by single-stranded adeno-associated viral vectors of serotypes 6, 8 and 9.

AIMS/HYPOTHESIS: The genetic engineering of pancreatic beta cells could be a powerful tool for examining the role of key genes in the cause and treatment of diabetes. Here we performed a comparative study of the ability of single-stranded (ss) adeno-associated viral vectors (AAV) of serotypes 6, 8 and 9 to transduce the pancreas in vivo. METHODS: AAV6, AAV8 and AAV9 vectors encoding marker genes were delivered to the pancreas via intraductal or systemic administration. Transduced cells were analysed by immunostaining. AAV9 vectors encoding hepatocyte growth factor (HGF) were delivered intraductally to a transgenic mouse model of type 1 diabetes and glycaemia was monitored. RESULTS: AAV6, AAV8 and AAV9 mediated efficient and long-term transduction of beta cells, with AAV6 and AAV8 showing the highest efficiency. However, alpha cells were poorly transduced. Acinar cells were transduced by the three serotypes tested and ductal cells only by AAV6. In addition, intraductal delivery resulted in higher AAV-mediated transduction of the pancreas than did systemic administration. As proof of concept, intraductal delivery of AAV9 vectors encoding for the beta cell anti-apoptotic and mitogenic HGF preserved beta cell mass, diminished lymphocytic infiltration of the islets and protected mice from autoimmune diabetes. CONCLUSIONS/INTERPRETATION: Intraductal administration of AAV6, AAV8 and AAV9 is an efficient way to genetically manipulate the pancreas in vivo. This technology may prove useful in the study of islet physiopathology and in assessment of new gene therapy approaches designed to regenerate beta cell mass during diabetes.

High AAV vector purity results in serotype- and tissue-independent enhancement of transduction efficiency.

The purity of adeno-associated virus (AAV) vector preparations has important implications for both safety and efficacy of clinical gene transfer. Early-stage screening of candidates for AAV-based therapeutics ideally requires a purification method that is flexible and also provides vectors comparable in purity and potency to the prospective investigational product manufactured for clinical studies. The use of cesium chloride (CsCl) gradient-based protocols provides the flexibility for purification of different serotypes; however, a commonly used first-generation CsCl-based protocol was found to result in AAV vectors containing large amounts of protein and DNA impurities and low transduction efficiency in vitro and in vivo. Here, we describe and characterize an optimized, second-generation CsCl protocol that incorporates differential precipitation of AAV particles by polyethylene glycol, resulting in higher yield and markedly higher vector purity that correlated with better transduction efficiency observed with several AAV serotypes in multiple tissues and species. Vectors purified by the optimized CsCl protocol were found to be comparable in purity and functional activity to those prepared by more scalable, but less flexible serotype-specific purification processes developed for manufacture of clinical vectors, and are therefore ideally suited for pre-clinical studies supporting translational research.

Impact of irrigation with arsenic-rich groundwater on soils and crops.

The study was carried out in an intensively cultivated agricultural area of central Spain where high arsenic (As) concentrations in groundwater were previously reported. The concentrations and distribution of As in soils and crops (wheat, potato, sugar beet and carrot) were determined to know the effect of irrigation with As-rich groundwater in the agricultural fields, and to estimate its impact on the food chain contamination. Irrigation water shows high As concentrations ranging between 38 and 136 microg/l. Total As contents in the studied agricultural soils are higher than 10 mg/kg exceeding the As content in two control areas and the results of this study reflect that irrigation with As-rich groundwater led to the elevated As levels in the agricultural soils. Total As concentration in soils of a sugar beet plot (36 mg/kg) is higher than that found in soils of the less intensively watered field (11 mg/kg), and more than 3.5 times higher than that in the soils of the control area irrigated with uncontaminated water (<10 mg/kg). Water soluble As in soils ranges between 0.03 and 0.9 mg/kg exceeding the limit of 0.04 mg/kg for agricultural use and shows a significant correlation with total As and organic matter (OM) content in soils. Arsenic contents in potato tuber samples are 35 times higher than that measured in potato tuber of uncontaminated control sites (0.03 mg/kg). Elevated As contents (3.9-5.4 mg/kg DW) were also found in root samples of sugar beet. The As contents in vegetable samples are higher than As content (0.1 mg/kg DW) in plants of uncontaminated control areas, and the limits for foodstuffs (0.5-1 mg/kg DW) set by legislation of many countries reflecting the risk of food chain contamination by As in this study area.

Characterization of secondary products in arsenopyrite-bearing mine wastes: influence of cementation on arsenic attenuation.

The secondary products of an arsenopyrite-bearing mine waste dump were characterized in order to ascertain their mineralogical, chemical and environmental features and to appraise their role in the abatement of As in the environment. To this purpose, representative surface samples of weathered sulfides (including cemented phases) and hardpan samples were collected and studied by X-ray powder diffraction (XRD), polarized light microscopy, electron microprobe analysis (EMPA), micro-Raman spectroscopy and digestion, extraction and leaching methods. Scorodite, amorphous ferric arsenates (AFA), elemental sulfur, hydronium jarosite, goethite, hematite and hydrous ferric oxides were the secondary products identified in the mine wastes. The hardpan was mainly constituted by gangue minerals, including sulfides (arsenopyrite and pyrite/marcasite) with different weathering degrees, cemented by cracked yellow phases corresponding to AFA with Fe/As molar ratios of 1.14-1.85 and elemental sulfur. These cracked compounds were also the binding agent in the other cemented phases. Hydronium jarosite and Fe (oxyhydr)oxides were enriched in As, showing values of 0.19-3.98 and 0.81-7.49 wt.% As2O5, respectively. The As leachability and lability from hardpan and cemented phases were not decreased as compared to those from the other weathered phases not showing cementation in the mine waste dump.

Risk minimisation of FGD gypsum leachates by incorporation of aluminium sulphate.

The incorporation of aluminium sulphate to (flue gas desulphurisation) FGD gypsum before its disposal was investigated as a way to minimise the risk supposed by the high fluoride content of its leachates. Using a bath method the kinetic and equilibrium processes of fluoride removal by aluminium sulphate were studied at fluoride/aluminium molar concentration (F/Al) ratios in the range 1.75 10(-2)-1.75 under the pH conditions (about 6.5) of FGD gypsum leachates. It was found that fluoride removal was a very fast process at any of the (F/Al) ratios subject of study, with equilibrium attained within the first 15 min of interaction. High decreases in solution fluoride concentrations (50-80%) were found at the equilibrium state. The use of aluminium sulphate in the stabilization of FGD gypsum proved to greatly decrease its fluoride leachable content (in the range 20-90% for aluminium sulphate doses of 0.1-5%, as determined by the European standard EN 12457-4). Such fluoride leaching minimisation assures the characterization of this by-product as a waste acceptable at landfills for non-hazardous wastes according to the Council Decision 2003/33/EC on waste disposal. Furthermore, as derived from column leaching studies, the proposed stabilization system showed to be highly effective in simulated conditions of disposal, displaying fluoride leaching reduction values about 55 and 80% for aluminium sulphate added amounts of 1 and 2%, respectively.

Study of the use of coal fly ash as an additive to minimise fluoride leaching from FGD gypsum for its disposal.

The use of coal fly ash as a fluoride retention additive has been studied as a way of treating flue gas desulphurisation (FGD) gypsum for its disposal in landfills. With this end leaching studies following the standard EN-12457-4 [Characterization of waste- Leaching-Compliance test for leaching of granular waste materials and sludges - Part 4: One stage batch test at a liquid to solid ratio of 10l/kg for materials with particle size below 10mm (without or with size reduction)] have been performed on FGD gypsum samples treated with different proportions of fly ash (0.1-100%). It was found that the fluoride leachable content in FGD gypsum was reduced in the range 1-55%, depending on the fly ash proportion added to FGD gypsum. High levels of fluoride leaching reduction (close to 40%) were achieved even at relatively low fly ash additions (5%). So, low fly ash incorporations assure the characterization of this by-product as a waste acceptable at landfills for non-hazardous wastes according to the Council Decision 2003/33/EC [Council Decision 2003/33/EC of 19 December 2002 establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC] on waste disposal. Furthermore, the effectiveness of the proposed FGD gypsum stabilization method was also studied in column leaching systems, proving its good performance in simulated conditions of disposal. In such conditions a fluoride leaching reduction value slightly higher than 25% was displayed for a fly ash added amount of 5%.

Implications of moisture content determination in the environmental characterisation of FGD gypsum for its disposal in landfills.

The leachable contents of elements of environmental concern considered in the Council Decision 2003/33/EC on waste disposal were determined in flue gas desulphurisation (FGD) gypsum. To this end, leaching tests were performed following the standard EN-12457-4 which specifies the determination of the dry mass of the material at 105 degrees C and the use of a liquid to solid (L/S) ratio of 10l kg(-1) dry matter. Additionally, leaching tests were also carried out taking into account the dry mass of the material at 60 degrees C and using different L/S ratios (2, 5, 8, 10, 15 and 20l kg(-1) dry matter). It was found that the dry mass determination at 105 degrees C turns out to be inappropriate for FGD gypsum since at this temperature gypsum transforms into bassanite, and so, in addition to moisture content, crystalline water is removed. As a consequence the moisture content is overvalued (about 16%), what makes consider a lower L/S ratio than that specified by the standard EN-12457-4. As a result the leachable contents in FGD gypsum are, in general, overestimated, what could lead to more strict environmental requirements for FGD gypsum when considering its disposal in landfills, specially concerning those elements (e.g., F) risking the characterisation of FGD gypsum as a waste acceptable at landfills for non-hazardous wastes.

Environmental, physical and structural characterisation of geopolymer matrixes synthesised from coal (co-)combustion fly ashes.

The synthesis of geopolymer matrixes from coal (co-)combustion fly ashes as the sole source of silica and alumina has been studied in order to assess both their capacity to immobilise the potentially toxic elements contained in these coal (co-)combustion by-products and their suitability to be used as cement replacements. The geopolymerisation process has been performed using (5, 8 and 12 M) NaOH solutions as activation media and different curing time (6-48 h) and temperature (40-80 degrees C) conditions. Synthesised geopolymers have been characterised with regard to their leaching behaviour, following the DIN 38414-S4 [DIN 38414-S4, Determination of leachability by water (S4), group S: sludge and sediments. German standard methods for the examination of water, waste water and sludge. Institut für Normung, Berlin, 1984] and NEN 7375 [NEN 7375, Leaching characteristics of moulded or monolithic building and waste materials. Determination of leaching of inorganic components with the diffusion test. Netherlands Normalisation Institute, Delft, 2004] procedures, and to their structural stability by means of compressive strength measurements. In addition, geopolymer mineralogy, morphology and structure have been studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. It was found that synthesised geopolymer matrixes were only effective in the chemical immobilisation of a number of elements of environmental concern contained in fly ashes, reducing (especially for Ba), or maintaining their leachable contents after the geopolymerisation process, but not for those elements present as oxyanions. Physical entrapment does not seem either to contribute in an important way, in general, to the immobilisation of oxyanions. The structural stability of synthesised geopolymers was mainly dependent on the glass content of fly ashes, attaining at the optimal activation conditions (12 M NaOH, 48 h, 80 degrees C) compressive strength values about 60 MPa when the fly ash glass content was higher than 90%.

Stabilization of FGD gypsum for its disposal in landfills using amorphous aluminium oxide as a fluoride retention additive.

The applicability of amorphous aluminium oxide as a fluoride retention additive to flue gas desulphurisation (FGD) gypsum was studied as a way of stabilizing this by-product for its disposal in landfills. Using a batch method the sorption behaviour of amorphous aluminium oxide was evaluated at the pH (about 6.5) and background electrolyte conditions (high chloride and sulphate concentrations) found in FGD gypsum leachates. It was found that fluoride sorption on amorphous aluminium oxide was a very fast process with equilibrium attained within the first half an hour of interaction. The sorption process was well described by the Langmuir model, offering a maximum fluoride sorption capacity of 61.7 mg g(-1). Fluoride sorption was unaffected by chloride co-existing ions, while slightly decreased (about 20%) by competing sulphate ions. The use of amorphous aluminium oxide in the stabilization of FGD gypsum proved to greatly decreased its fluoride leachable content (in the range 5-75% for amorphous aluminium oxide doses of 0.1-2%, as determined by the European standard EN 12457-4 [EN-12457-4 Characterization of waste-leaching-compliance test for leaching of granular waste materials and sludges-Part 4: one stage batch test at a liquid to solid ratio of 10 l/kg for materials with particle size below 10mm (without or with size reduction)]), assuring the characterization of this by-product as a waste acceptable at landfills of non-hazardous wastes according to the Council Decision 2003/33/EC [Council Decision 2003/33/EC of 19 December 2002. Establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC] on landfill of wastes. Furthermore, as derived from column leaching studies, the proposed stabilization system proved to be highly effective in simulated conditions of disposal, displaying a fluoride leaching reduction value about 81% for an amorphous aluminium oxide added amount of 2%.

Removal of cadmium from aqueous solutions by palygorskite.

The sorption characteristics of palygorskite with respect to cadmium were studied with the aim of assessing its use in water purification systems. Using a batch method the influence of time (0.5-48 h), initial Cd concentration (5-150 mg/l or 0.044-1.34 mmol/l), ionic strength ([Ca(II)]: 0-0.1 mol/l), pH (3-7) and mineral dose (1-20 g/l) on Cd removal was evaluated. The sorption of Cd on palygorskite appeared as a fast process, with equilibrium being attained within the first half an hour of interaction. This process could be described by the Langmuir model and gave a maximum Cd sorption of 4.54 mg/g. This sorption capacity value was greatly affected by both pH and ionic strength. Thus, Cd sorption decreased as initial pH lessened, especially at proton concentrations similar to those of Cd, at which competition for variable charge sites (silanol groups on palygorskite surface) appeared to be important. High competing electrolyte concentrations also decreased significantly (close to 60%) the amount of sorbed Cd, suggesting a great contribution of replacement of exchange cations in this metal removal by palygorskite. The increase of mineral dose provoked a Cd removal raise; removal values in the range 85-45% were attained for Cd initial concentrations of 10-150 mg/l (0.089-1.34 mmol/l) when a palygorskite dose of 20 g/l was employed. Column studies were also performed in order to estimate the potential of palygorskite to be used in continuous flow purification systems, showing the effectiveness of this mineral to purify down to the legal limit of waste moderate volumes of Cd-containing solutions with a similar concentration (50mg/l or 0.445 mmol/l) to those mostly found in the upper range of concentrations usually present in industrial wastewaters.

Adsorption of Cr(VI) from synthetic solutions and electroplating wastewaters on amorphous aluminium oxide.

The adsorption behaviour of amorphous aluminium oxide was studied with respect to Cr(VI) in order to consider its application to purify electroplating wastewaters. A batch method was employed using Cr(VI) concentrations ranged from 10 to 200mg/l. The Langmuir model was found to describe the adsorption process well, offering a maximum adsorption capacity of 78.1mg/g. The effect of ionic strength (0-0.1M KNO(3)), pH (3-9) and competitive solutes (molar ratio [Cr(VI)]/[SO(4)(2-)]=1 and 100) on the retention process was evaluated. Cr(VI) adsorption on amorphous aluminium oxide appeared to be dependent on ionic strength with a more pronounced effect in acid conditions. Conversely, adsorption was not affected by pH in acid medium, but decreased when pH sifted to alkaline values. The presence of SO(4)(2-) greatly reduced Cr(VI) removal across the entire pH range when both solutes were present in similar concentrations. Amorphous aluminium oxide also showed a high adsorption capacity when used in the purification of Cr(VI) electroplating wastewaters. The adsorbent doses required to attain more than 90% of Cr(VI) removal varied between 1 and 5 g/l depending on Cr(VI) concentration in wastewaters.

Trace element levels in an area impacted by old mining operations and their relationship with beehive products.

The environmental status of an area impacted by Roman mining activities was assessed in order to establish the current risks posed by such old mine emplacements. For this purpose, soil samples were collected throughout the mining area and analysed for their total, mobile and mobilizable trace element (As, Cd, Mo, Sb and Zn) contents. Additionally, beehive products (honey and pollen) were also sampled and evaluated for their use as environmental indicators of the area. The results obtained were compared with those from a control non-polluted area. The mine soils presented slightly increased levels of Cd and Sb (about 2- to -3-fold their normal soil concentrations), whereas the enrichment of As reached considerable levels, with concentrations almost ten-fold of those considered the threshold for causing toxicity. Leachable As contents exhibited very high values (1.2-21.9mgkg-1), indicating the need for risk attenuation measures. All trace elements were mainly partitioned in the soil residual fraction, especially Mo (76-99%) and Sb (61-91%). Significant partitioning levels were also found in the reducible fraction of As (up to 35%) and Cd (up to 38%), and in the oxidizable fraction of Mo (up to 23%). The reducible pool of As was particularly relevant due to the eventual mobilization of this element under reducing conditions. Among the beehive products tested, honey proved not to be useful as an environmental indicator, whereas pollen showed great potential as an indicator when the contamination levels were moderate to high.

Emission reduction of aluminium anodising industry by production of Mg2+-Al3+-SO4(2-) -hydrotalcite-type compound.

The synthesis of Mg(2+)-Al(3+)-SO(4)(2-)-hydrotalcite-type compound from the acid wastewaters of the aluminium anodising industry has been studied as a possible way of reducing the emissions to the environment, recovering simultaneously resource materials as a valuable mineral. The process of synthesis was carried out using rinse wastewater solutions generated from the anodising treatment when a cascade rinsing system is employed. The method of co-precipitation at constant pH was employed for such a process, using MgO as a source of magnesium. The synthesis was studied as a function of precipitation pH (8-10) and flow rate of reagent mixture (5-30 ml min(-1)). High pH of precipitation and low flow rate of reagent mixture (5-15 ml min(-1)) were found optimal to improve the crystallinity of the synthesised product. The mineral characterisation was performed using X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis and differential thermal analysis, all of which indicated characteristics typical of the desired compound. Almost 100% of the aluminium initially present in the acid wastewater solutions was recovered in the form of Mg(2+)-Al(3+)-SO(4)(2-)-hydrotalcite-type compound.

Environmental impact of a coal combustion-desulphurisation plant: abatement capacity of desulphurisation process and environmental characterisation of combustion by-products.

The fate of trace elements in a combustion power plant equipped with a wet limestone flue gas desulphurisation (FGD) installation was studied in order to evaluate its emission abatement capacity. With this aim representative samples of feed coal, boiler slag, fly ash, limestone, FGD gypsum and FGD process water and wastewater were analysed for major and trace elements using the following techniques: inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), ion chromatography (IC), ion selective electrode (ISE) and atomic absorption spectroscopy (AAS). Mass balances were established allowing to determine the element partitioning behaviour. It was found that, together with S, Hg, Cl, F, Se and As were those elements entering in the FGD plant primarily as gaseous species. The abatement capacity of the FGD plant for such elements offered values ranged from 96% to 100% for As, Cl, F, S and Se, and about 60% for Hg. The environmental characterisation of combustion by-products (boiler slag, fly ash and FGD gypsum) were also established according to the Council Decision 2003/33/EC on waste disposal. To this end, water leaching tests (EN-12457-4) were performed, analysing the elements with environmental concern by means of the aforementioned techniques. According to the leaching behaviour of combustion by-products studied, these could be disposed of in landfills for non-hazardous wastes.

Evaluation of the turnaround time of an integrated preanalytical and analytical automated modular system in a medium-sized laboratory.

OBJECTIVES: Evaluation of an integrated Modular Preanalytics (MPA) and Modular Analytics SWA (MA) system (Roche Diagnostics) during continuous batch processing. DESIGN AND METHODS: A total of 1000 blood specimen tubes was processed and tested in a batch-wise fashion, according to two different specimen input conditions (Study 1 and Study 2). The resulting turnaround time of the system was assessed. RESULTS: Study 1 tubes were centrifuged in the MPA. The preanalytical time rose steadily from 14 to 28 min, and after sample 315, it showed minimal variation. The analytical time remained almost constant. In Study 2, tubes were centrifuged before being processed in the MPA. The preanalytical time increased from 4 to 19 min, and the analytical time increased similarly. The turnaround time in Study 1 was 132 min and in Study 2 was 108 min. CONCLUSION: Centrifugation in the MPA slightly increased the turnaround time. Nevertheless, the labor associated with specimen processing was reduced and the efficiency of the laboratory was improved.