Background, aim, and scope The success of phytoextraction depends upon the identification of suitable plant species that hyperaccumulate heavy metals and produce large amounts of biomass using established agricultural techniques. In this study, the Mediterranean saltbush Atriplex halimus L., which is a C4 perennial native shrub of Mediterranean basin with an excellent tolerance to drought and salinity, is investigated with the main aim to assess its phytoremediation potential for Pb and Cd removal from contaminated soils. In particular, the influence of soil salinity in metal accumulation has been studied as there is notable evidence that salinity changes the bioavailability of metals in soil and is a key factor in the translocation of metals from roots to the aerial parts of the plant. Materials and methods Three pot experiments were conducted under greenhouse conditions for a 10-week period with A. halimus grown in soil artificially polluted with 20 ppm of Cd and/or 800 ppm of Pb and irrigated with three different salt solutions (0.0%, 0.5%, and 3.0% NaCl). Soil measurements for soil characterization were performed with the expiration of the first week of plant exposure to metals and NaCl, and at the end of the experimental period, chlorophyll content, leaf protein content, leaf specific activity of guaiacol peroxidase (EC 1.11.1.7), shoot water content, biomass, and Cd and Pb content in the plant tissues were determined. Additionally, any symptoms of metal or salt toxicity exhibited by the plants were visually noted during the whole experimental period. Results The experimental data suggest that increasing salinity increases cadmium uptake by A. halimus L. while in the case of lead there was not a clear effect of the presence of salt on lead accumulation in plant tissues. A. halimus developed no visible signs of metal toxicity; only salt toxicity symptoms were observed in plants irrigated with 3% NaCl solutions. Chlorophyll content, leaf protein content, shoot water content, and biomass were not negatively affected by the metals; instead, there was even an increase in the amount of photosynthetic pigments in plants treated with both metals and salinity. The specific activity of guaiacol peroxidase seems to have a general tendency for increase in plants treated with the metals in comparison with the respective controls but a statistically significant difference exists only in plants treated with the metal mixture and saline conditions. Discussion The data revealed that lead and cadmium accumulation in plant tissues was kept generally at low levels. Salinity was found to have a positive effect on cadmium uptake by the plant and this may be related to a higher bioavailability of the metal in soil due to decreased Cd sorption on soil particles. On the other hand, salinity did not influence in a clear way the uptake of Pb by the plant probably because of lead's limited mobility in soils and plant tissues. Cd and Pd usually decrease the chlorophyll content and biomass and change water relations in plants; however, A. halimus was found not to be affected indicating that it is a Cd- and Pb-tolerant plant. Guaiacol peroxidase activity as one of the parameters expressing oxidative damage and extent of stress in plants was not generally found to be significantly affected under the presence of metals in most plants suggesting that the extent of stress in plants was minimal, while only for plants treated with the metal mixture and low salinity the enzyme activity was elevated confirming that this enzyme serves as an antioxidative tool against the reactive oxygen species produced by the metals. Conclusions Atriplex halimus L. is a Pb- and Cd-tolerant plant but metal concentrations achieved in plant tissues were kept generally at low levels; however, metal accumulation in shoots, especially for Cd, considered together with its high biomass production, rapid growth, and deep root system able to cope with poor structure and xeric characteristics of several polluted soils suggest that this plant deserves further investigation. Recommendations and perspectives Phytoextraction by halophytes is a promising alternative for the remediation of heavy metal contaminated sites affected by salinity since saline depressions often indicate sites of industrial effluents accumulation, contaminated by heavy metals, including Pb and Cd. Halophytes are also promising candidates for the removal of heavy metals from non-saline soils. Furthermore, the use of such plants can be potentially viewed as an alternative method for soil desalination where salt is removed from the soil instead of being washed downwards by water or other solutions.

Background, aim and scope The external surface of any building in urban polluted environment is unavoidably destined to be covered with layers that assume a grey to black colour and are generally called 'black crusts'. These, according to standard protocols and glossary, are deteriorated surface layers of stone material; they can have variable thickness, are hard and fragile and can detach spontaneously from the substrate, which, in general, is quite decayed. Plain visual examination may lead to consider 'black crusts' all similar, whilst only a careful diagnostic investigation can distinguish 'black crusts' and the consequences of their formation on stone substrates. In this paper, various black layers on marble are studied and compared and the morphological and compositional characteristics discussed according to the related mechanisms of formation. Differences between old (hundred years) and recent crusts (30 years) are investigated and pointed out. Materials and methods Samples of black crusts collected from the Milan Cathedral façade (Candoglia Marble) have been studied and compared with the careful and synergic employ of traditional techniques: optical (transmission and reflected VIS light) and electron microscopy, X-ray spectrometry and micro-Fourier transform infrared spectroscopy. Results Visual examination of loose fragments does not allow to point out outstanding differences amongst the various samples; black layers have similar main mineral components, gypsum and airborne particles, with different spatial distribution. The microscopic studies allowed to point out the porosity differences, the gypsum crystallisation habit, different amount of embedded particles, level and progress of marble decay. Discussion The observations lead to define three main types of black crusts: black crust deriving from marble sulphation, compact deposit and encrustation due to exogenic materials deposition. Black crusts show evidence of sulphation in progress, without a clear continuity solution between crust and marble; the lack of separation is particularly evident in 'recent' crust, where the sulphation process is more active. Black compact deposits show a higher porosity than black crusts because gypsum is not coming from the chemical corrosion of the substrate but from outside; actually, in the former case, the substrate is sound. Encrustations show a highly regular crystal organisation of gypsum (close packed tabular crystals) that cannot be traced back to casual atmospheric deposit or to corrosion of the substrate but rather to the crystallisation of a solution coming from an external source. Also in this case, the marble is sound; evidence of the effect of some protection treatment is pointed out. Conclusions In spite of the apparent similarity of the examined samples, analytical results have evidenced three main types of black crusts: black crust with decayed substrate, compact deposit and black encrustation showing a sound substrate underneath. Experimental evidence of calcite grains sulphation in progress, taking place according to a model recently proposed, has been observed. Sulphation process is prevented where particular conservation treatments had been applied in the past. Recommendations and perspectives New experimental studies can be focussed to understand the specific conditions (measurements of micro-climatic and thermodynamic parameters) and mechanisms for black crusts formation in situ. The problem of the kinetic of the sulphation process of marble, the assessment of black layers formation in the case of different carbonate stone materials and the study of acid attack in presence of surface protecting layers deserve further investigation.

Background, aim and scope Each year, large quantities of pharmaceuticals are consumed worldwide for the treatment and prevention of human and animal diseases. Although the drugs and the metabolites observed in the wastewaters and in the environment are present at concentrations several orders of magnitude lower than the concentrations required to exert their effects in humans or animals, their long-term impact on the environment is commonly not known. In this study, the occurrence of six antihistamines, which are used for the relief of allergic reactions such as hay fever, was determined in sewage treatment plants wastewaters and in recipient river waters. Materials and methods The occurrence of the antihistamines cetirizine, acrivastine, fexofenadine, loratadine, desloratadine and ebastine in sewage treatment plants wastewaters and in recipient river waters was studied. The analytical procedure consisted of solid-phase extraction of the water samples followed by liquid chromatography separation and detection by a triple-quadrupole mass spectrometer in the multiple reaction mode. Results Cetirizine, acrivastine and fexofenadine were detected in both influent and effluent wastewater samples at concentration levels ranging from about 80 to 220 ng/L, while loratadine, desloratadine and ebastine could not be detected in any samples. During sewage treatment, the concentration of the antihistamines dropped by an average of 16-36%. Furthermore, elevated concentrations of antihistamines were observed in samples collected during the season of most intensive plant pollen production, i.e. in May. In the river water samples, the relative pattern of occurrence of cetirizine, acrivastine and fexofenadine was similar to that in the wastewater samples; although the concentration of the compounds was substantially lower (4-11 ng/L). The highest concentrations of the studied drugs were observed near the discharging point of the sewage treatment plant. Discussion The highest concentrations of antihistamines in STP wastewaters correlate with the outbreak of allergic reaction caused by high amounts of plant pollens in the air. The analysis results of the river water samples show that the antihistamines are carried far away from the effluent discharge points. They may account for a part of the mix of pharmaceuticals and of pharmaceutical metabolites that occur downstream of STPs. Conclusions Antihistamines are poorly degraded/eliminated under the biological treatment processes applied in the wastewater treatment plants and, consequently, they are continuously being discharged along with other drugs to the aquatic environment. Recommendations and perspectives As a huge quantity and variety of drugs and their metabolites are continuously discharged to rivers and the sea, the compounds should be considered as contaminants that may possess risks to the aquatic ecosystem. Further studies are urgently needed on the environmental fate of the antihistamines and other pharmaceuticals in the aquatic environment. These studies should be concerned with the stability of the compounds, their transformation reactions and the identity of the transformation products, the distribution of drugs and their uptake and effects in organisms. On the basis of these studies, the possible environmental hazards of pharmaceuticals may be assessed.

Introduction Several hot spots of severe freshwater pollution and sediment contamination (mostly heavy metals, polyaromatic hydrocarbons and polychlorinated biphenyls) have been identified in Serbia as the consequence of outdated environmental legislation, negligible amounts of properly treated waste waters and accidental spills. Discussion Since ecotoxicological methods have never been incorporated into risk assessment procedures, mandatory effluent discharge or ambient water monitoring programmes, ecotoxicological research, based on bioaccumulation studies, conventional ecotoxicological tests and, recently, biomarkers of exposure and effect have been restricted to independent small- to medium-scale studies, conducted, basically, to confirm, underline or oppose the results of chemical-based monitoring and to lament on inadequate environmental regulations/policy and management practice. Although hot and unresolved ecotoxicological problems still remain beyond the reach of ecotoxicological research currently conducted in Serbia, or are tackled only sporadically, it is to be expected that on-going research and institutional capacity building should, hopefully, increase the competence and competitiveness of scientific community and speed up the process of harmonisation of national environmental legislation and policy with European Union.

Background, aim and scope One of the problems to affect Portland cement matrices is low resistance to aggressive agents, due principally to the presence of a high content of portlandite in the hydrated cements. Pozzolanic materials have played an important role in the improving the durability of cement-based materials for decades. This work studies the behaviour of cement mortar matrices blended with 10% calcined paper sludge (source for metakaolinite) and exposed to different environmental conditions (saline and non-saline environments) after 6 and 12 months of exposure. Materials and methods Two cements were studied: an ordinary Portland cement (CEM 1, 42.5R), acting as reference cement, and a blended cement formulated by mixing 90% (by mass) of CEM 1, 42.5R with 10% (by mass) of paper sludge calcined at 700°C for 2 h. The specimens were exposed 1 year to saline and non-saline environments. All the mineralogy samples were studied through X-ray diffraction and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray analyser. The in-depth study on ionic mobility was performed on samples subjected to natural exposure (coast and tableland) for 6 and 12 months. Results Portland cement was composed of quartz, calcite, calcium hydroxide and tobermorite gels. The pozzolanic cement (10% calcined paper sludge) is of the same composition but a high calcite concentration and barium carbonate. SEM analysis from coastline show deposits of variable composition. The deposits are identified on the surface of different mineral components. The minerals from tableland are much fractured, i.e. calcite and feldspars. Inside the fractures, the deposits and the ions are located and trapped superficially. Discussion SEM analysis of control cement Portland and 10% calcined paper sludge shows deposits on quartz and calcite with a very high concentration of Pb, Zn, Cl and barium sulphate. A very porous aspect is due to the presence of the different aggregate types. This porous configuration permits retention of the ion environment. The pozzolanic cement in environments subject to the saline mist favours the retention and transport of ions observed. Something similar also happens with the increase in exposure to outdoor weather. Non-saline samples show temperature changes (ice or thaw cycles). Barium retention is kept on the surface in fracture lines by the gelification processes. In general, it may be inferred that an increase in exposure time increases the diffusion of ions towards test piece interiors. The chemical composition profiles show that the ions present different penetration speeds. Conclusions The results indicate the better vulnerability of pozzolanic cements from calcined paper sludge in saline and non-saline environments. The cements with a 10% addition of calcined paper sludge favour retention and transport of ion has been observed. Recommendations and perspectives Today, projects are centred on a new recycling line for industrial waste of this kind, with special attention on its incorporation in cement manufacture as a pozzolanic material, setting the most appropriate activation conditions of the mineralogical compound in this waste (kaolinite and metakaolinite) and taking them as a starting point for this project. The use of pozzolanic cement with 10% addition of calcined paper sludge is a system which favours ionic retention.

Background, aim and scope In the region of the Apuseni Mountains, part of the Western Carpathians in Romania, metal mining activities have a long-standing tradition. These mining industries created a clearly beneficial economic development in the region. But their activities also caused impairments to the environment, such as acid mine drainage (AMD) resulting in long-lasting heavy metal pollution of waters and sediments. The study, established in the context of the ESTROM programme, investigated the impact of metal mining activities both from environmental and socioeconomic perspectives and tried to incorporate the results of the two approaches into an integrated proposition for mitigation of mining-related issues. Study site The small Certej catchment, situated in the Southern Apuseni Mountains, covers an area of 78 km². About 4,500 inhabitants are living in the basin, in which metal mining was the main economic sector. An open pit and several abandoned underground mines are producing heavy metal-loaded acidic water that is discharged untreated into the main river. The solid wastes of mineral processing plants were deposited in several dumps and tailings impoundment embodying the acidic water-producing mineral pyrite. Methods The natural science team collected samples from surface waters, drinking water from dug wells and from groundwater. Filtered and total heavy metals, both after enrichment, and major cations were analysed by inductively coupled plasma optical emission spectroscopy (ICP-OES). Major anions in waters, measured by ion chromatography, alkalinity and acidity were determined by titration. Solid samples were taken from river sediments and from the largest tailings dam. The latter were characterised by X-ray fluorescence and X-ray diffraction. Heavy metals in sediments were analysed after digestion. Simultaneously, the socioeconomic team performed a household survey to evaluate the perception of people related to the river and drinking water pollution by way of a logistic regression analysis. Results and discussion The inputs of acid mine waters drastically increased filtered heavy metal concentrations in the Certej River, e.g. Zn up to 130 mg L⁻¹, Fe 100 mg L⁻¹, Cu 2.9 mg L⁻¹, Cd 1.4 mgL⁻¹ as well as those of SO₄ up to 2.2 g L⁻¹. In addition, river water became acidic with pH values of pH 3. Concentrations of pollutant decreased slightly downstream due to dilution by waters from tributaries. Metal concentrations measured at headwater stations reflect background values. They fell in the range of the environmental quality standards proposed in the EU Water Framework Directive for dissolved heavy metals. The outflow of the large tailing impoundment and the groundwater downstream from two tailings dams exhibited the first sign of AMD, but they still had alkalinity. Most dug wells analysed delivered a drinking water that exhibited no sign of AMD pollution, although these wells were a distance of 7 to 25 m from the contaminated river. It seems that the Certej River does not infiltrate significantly into the groundwater. Pyrite was identified as the main sulphide mineral in the tailings dam that produces acidity and with calcite representing the AMD-neutralising mineral. The acid-base accounting proved that the potential acid-neutralising capacity in the solid phases would not be sufficient to prevent the production of acidic water in the future. Therefore, the open pits and mine waste deposits have to be seen as the sources for AMD at the present time, with a high long-term potential to produce even more AMD in the future. The socioeconomic study showed that mining provided the major source of income. Over 45% of the households were partly or completely reliant on financial compensations as a result of mine closure. Unemployment was considered by the majority of the interviewed persons as the main cause of social problems in the area. The estimation of the explanatory factors by the logistic regression analysis revealed that education, household income, pollution conditions during the last years and familiarity with environmental problems were the main predictors influencing peoples' opinion concerning whether the main river is strongly polluted. This model enabled one to predict correctly 77% of the observations reported. For the drinking water quality model, three predictors were relevant and they explained 66% of the observations. Conclusions Coupling the findings from the natural science and socioeconomic approaches, we may conclude that the impact of mining on the Certej River water is high, while drinking water in wells is not significantly affected. The perceptions of the respondents to pollution were to a large extent consistent with the measured results. Recommendations and perspectives The results of the study can be used by various stakeholders, mainly the mining company and local municipalities, in order to integrate them in their post-mining measures, thereby making them aware of the potential long-term impact of mining on the environment and on human health as well as on the local economy.

Background, aim, and scope Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate. Materials and methods The decay of the organics was followed using in situ Fourier transform infrared spectroscopy and the rate coefficients were determined using a relative kinetic method and different hydrocarbon reference compounds. Results The following room temperature rate coefficients (in cm³ molecule⁻¹ s⁻¹) were obtained: k ₁ (Cl + CH₃C(O)OCH=CH₂) = (2.68 ± 0.91) x 10⁻¹⁰, k ₂ (Cl + CH₃C(O)OCH₂CH=CH₂) = (1.30 ± 0.45) x 10⁻¹⁰, and k ₃ (Cl + CH₂=CHC(O)O(CH₂)₃CH₃) = (2.50 ± 0.78) x 10⁻¹⁰, where the uncertainties are a combination of the 2σ statistical errors from linear regression analyses and a contribution to cover uncertainties in the rate coefficients of the reference hydrocarbons. Discussion This is the first kinetic study of the title reactions under atmospheric conditions. The kinetic data were analyzed in terms of reactivity trends and used to estimate the atmospheric lifetimes of the esters and assess their potential importance in the marine atmosphere. Conclusions Although reaction with OH radicals is the major atmospheric sink for the unsaturated esters studied, reaction with Cl atoms can compete in the early morning hours in coastal areas where the Cl concentration can reach peak values as high as 1 x 10⁵ atoms cm⁻³. The calculated residence times show that the chemistry of unsaturated esters will impact air quality locally near their emission sources. Recommendations and perspectives The reactions need to be studied over the range of temperatures and pressures generally encountered in the marine atmosphere. In addition, product studies should also be performed as a function of temperature since this will allow degradation mechanisms to be derived, which are representative for the wide range of conditions occurring in marine environments. Inclusion of the kinetic and product data in tropospheric numerical models will allow an assessment of potential environmental impacts of the esters for different marine pollution scenarios.

Background, aim, and scope The present study focuses on the temporal concentration changes of four common organic pollutants in small freshwater streams of Hesse, Germany. The substances (tris(2-chloroethyl)phosphate (TCEP), the technical isomer mixture of 4-nonylphenol (NP), 2-(t-butylamino)-4-(ethylamino)-6-(methylthio)-s-triazine (terbutryn), and N,N-diethyl-m-toluamide (DEET)) are subject to differing regulations. Whereas the use of NP and the related nonylphenolethoxylates (NPEOs) are almost completely banned under EU directive 2003/53/EC, the herbicide terbutryn is only restricted for use as a herbicide in the majority of member states of the European Union (EU). In contrast, TCEP and DEET are not regulated by legislation, but have been replaced in some products through consumer pressure. The impact of regulation on the environmental concentrations of these pollutants is discussed. Materials and methods The substances were monitored in small freshwater streams in the Hessisches Ried region, Germany, during the period September 2003 to September 2006. The samples were extracted with solid phase extraction (SPE) and analyzed by coupled gas chromatography-mass spectrometry (GC-MS). Results All target compounds were detected frequently within the fresh water streams of the study area. Monitoring in the study area revealed a significant concentration decrease only for NP. For the other three compounds, no significant concentration decrease was observed. Terbutryn concentrations and loads showed a seasonal trend with higher levels in summer and autumn, but were also present in winter and spring. Concentrations of TCEP and DEET were in the range of prior investigations. Discussion The decrease of NP concentrations and loads during the sampling period indicates that the regulation of NP and NP ethoxylates has led to a significant improvement in reducing the occurrence of this compound in the aquatic environment. Furthermore, the ban on agricultural use of terbutryn at the end of 2003 had no discernable influence on terbutryn concentrations in the following years. Conclusions The benefits of national bans or self-regulations by manufacturers on several chemicals appear to be limited. In contrast, the European-wide ban (of NP) revealed to be effective in preventing the substance from entering the aquatic environment on a large scale and reduced the NP concentration to an acceptable level (i.e., below the PNEC). Recommendations and perspectives Further research is needed to investigate diffuse sources and point sources of terbutryn not related to agriculture. Further research is required to find an explanation for the ongoing high concentration of TCEP in river water despite of the supposed replacement of TCEP by TCPP already in the 1990s.

Background, aim, and scope Composting is an effective treatment process to realize sludge land application. However, nitrogen loss could result in the reduction of nutrient value of the compost products and the stabilization effect of composting on heavy metal concentration and mobility in sludge has been shown to be very limited. Materials and methods Laboratory-scale experiments were carried out to investigate the effects of bamboo charcoal (BC) on nitrogen conservation and mobility of Cu and Zn during sludge composting. Results The result indicated that the incorporation of BC into the sludge composting material could significantly reduce nitrogen loss. With 9% BC amendment, total nitrogen loss at the end of composting decreased 64.1% compared with no BC amendment (control treatment). Mobility of Cu and Zn in the sludge may also have been lessened, based on the decline in diethylenetriaminepentaacetic acid-extractable Cu and Zn contents of composted sludge by 44.4% and 19.3%, respectively, compared to metal extractability in the original material. Discussion Ammonia adsorption capability of BC might be the main reason for the retention of nitrogen in sludge composting materials. Decrease of extractable Cu²⁺ and Zn²⁺ in the composting material mainly resulted from the adsorption of both metals by BC. Conclusions Incorporation of BC into composting material could significantly lessen the total nitrogen loss during sludge composting. Mobility of heavy metals in the sludge composting material could also be reduced by the addition of BC. Recommendations and perspectives Bamboo charcoal could be an effective amendment for nitrogen conservation and heavy metal stabilization in sludge composts. Further research into the effect of BC-amended sludge compost material on soil properties, bioavailability of heavy metals, and nutrient turnover in soil needs to be carried out prior to the application of BC-sludge compost in agriculture.

Background, aim, and scope The use of plants and associated microorganisms to remove, contain, inactivate, or degrade harmful environmental contaminants (generally termed phytoremediation) and to revitalize contaminated sites is gaining more and more attention. In this review, prerequisites for a successful remediation will be discussed. The performance of phytoremediation as an environmental remediation technology indeed depends on several factors including the extent of soil contamination, the availability and accessibility of contaminants for rhizosphere microorganisms and uptake into roots (bioavailability), and the ability of the plant and its associated microorganisms to intercept, absorb, accumulate, and/or degrade the contaminants. The main aim is to provide an overview of existing field experience in Europe concerning the use of plants and their associated microorganisms whether or not combined with amendments for the revitalization or remediation of contaminated soils and undeep groundwater. Contaminations with trace elements (except radionuclides) and organics will be considered. Because remediation with transgenic organisms is largely untested in the field, this topic is not covered in this review. Brief attention will be paid to the economical aspects, use, and processing of the biomass. Conclusions and perspectives It is clear that in spite of a growing public and commercial interest and the success of several pilot studies and field scale applications more fundamental research still is needed to better exploit the metabolic diversity of the plants themselves, but also to better understand the complex interactions between contaminants, soil, plant roots, and microorganisms (bacteria and mycorrhiza) in the rhizosphere. Further, more data are still needed to quantify the underlying economics, as a support for public acceptance and last but not least to convince policy makers and stakeholders (who are not very familiar with such techniques).