This study investigated the effects of pH (6–10) and ozone dose [0.4–3.0 mg O3/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85 ± 0.18 mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65 % fulvic and 14 % humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309 ± 15 μg/L). Ozonation at pH 6–10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65–90 % achieved using 3.0 mg O3/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH 10 (up to 68 % HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1 ± 6.0 μg/mg DOC in raw water to 152 ± 8 μg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH 10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.

Many pharmaceuticals and related metabolites are not efficiently removed in sewage treatment plants and enter into surface water. There, they might be subject of drinking water abstraction and treatment by ozonation. In this study, a systematic approach for producing and effect-based testing of transformation products (TPs) during the drinking water ozonation process is proposed. For this, two pharmaceutical parent substances, three metabolites and one environmental degradation product were investigated with respect to their biodegradability and fate during drinking water ozonation. The Ames test (TA98, TA100) was used for the identification of mutagenic activity present in the solutions after testing inherent biodegradability and/or after ozonation of the samples. Suspicious results were complemented with the umu test. Due to the low substrate concentration required for ozonation, all ozonated samples were concentrated via solid phase extraction (SPE) before performing the Ames test. With the exception of piracetam, all substances were only incompletely biodegradable, suggesting the formation of stable TPs. Metformin, piracetam and guanylurea could not be removed completely by the ozonation process. We received some evidence that technical TPs are formed by ozonation of metformin and piracetam, whereas all tested metabolites were not detectable by analytical means after ozonation. In the case of guanylurea, one ozonation TP was identified by LC/MS. None of the experiments showed an increase of mutagenic effects in the Ames test. However, the SPE concentration procedure might lead to false-positive results due to the generation of mutagenic artefacts or might lead to false-negative results by missing adequate recovery efficiency. Thus, these investigations should always be accompanied by process blank controls that are carried out along the whole ozonation and SPE procedure. The study presented here is a first attempt to investigate the significance of transformation products by a systematic approach. However, the adequacy and sensitivity of the methodology need to be further investigated. The approach of combining biodegradation and ozonation with effect-based assays is a promising tool for the early detection of potential hazards from TPs as drinking water contaminants. It can support the strategy for the evaluation of substances and metabolites in drinking water. A multitude of possible factors which influence the results have to be carefully considered, among them the selectivity and sensibility of the mutagenicity test applied, the extraction method for concentrating the relevant compounds and the biocompatibility of the solvent. Therefore, the results have to be carefully interpreted, and possible false-negative and false-positive results should be considered.

BACKGROUND, AIM AND SCOPE: Lead (Pb) accumulation in soils affects plants primarily through their root systems. The aim of this study was to investigate early symptoms of the loss of membrane integrity and lipid peroxidation in root tissues and physiological adaptation mechanism to Pb in accumulating ecotypes (AE) and non-accumulating ecotypes (NAE) of Sedum alfredii under Pb stress in hydroponics. METHODS AND RESULTS: Histochemical in situ analyses, fluorescence imaging, and normal physiological analysis were used in this study. Pb accumulation in roots of both AE and NAE increased linearly with increasing Pb levels (0–200 μM), and a significant difference between both ecotypes was noted. Both loss of plasma membrane integrity and lipid peroxidation in root tissues became serious with increasing Pb levels, maximum tolerable Pb level was 25 and 100 μM for NAE and AE, respectively. Pb supplied at a toxic level caused a burst of reactive oxygen species (ROS) in root cells in both ecotypes. However, the root cells of AE had inherently higher activities of superoxide dismutase (SOD), guaiacol peroxidase (POD), and lipoxygenase (LOX) in control plants, and the induction response of these antioxidant enzymes occurred at lower Pb level in AE than NAE. AE plants maintained higher ascorbic acid and H2O2 concentrations in root cells than NAE when exposed to different Pb levels, and Pb induced more increase in dehydroascorbate (DHA), catalase (CAT), and ascorbate peroxidase (APX) in AE than NAE roots. DISCUSSION AND CONCLUSION: Results indicate that histochemical in situ analyses of root cell death and lipid peroxidation under Pb short-term stress was sensitive, reliable, and fast. Higher tolerance in roots of accumulating ecotype under Pb stress did depend on effective free oxygen scavenging by making complex function of both constitutively higher activities and sensitive induction of key antioxidant enzymes in root cells of S. alfredii.

Numerous environmental chemicals, both long-known toxicants such as persistent organic pollutants as well as emerging contaminants such as pharmaceuticals, are known to modulate immune parameters of wildlife species, what can have adverse consequences for the fitness of individuals including their capability to resist pathogen infections. Despite frequent field observations of impaired immunocompetence and increased disease incidence in contaminant-exposed wildlife populations, the potential relevance of immunotoxic effects for the ecological impact of chemicals is rarely considered in ecotoxicological risk assessment. A limiting factor in the assessment of immunotoxic effects might be the complexity of the immune system what makes it difficult (1) to select appropriate exposure and effect parameters out of the many immune parameters which could be measured, and (2) to evaluate the significance of the selected parameters for the overall fitness and immunocompetence of the organism. Here, we present — on the example of teleost fishes — a brief discussion of how to assess chemical impact on the immune system using parameters at different levels of complexity and integration: immune mediators, humoral immune effectors, cellular immune defenses, macroscopical and microscopical responses of lymphoid tissues and organs, and host resistance to pathogens. Importantly, adverse effects of chemicals on immunocompetence may be detectable only after immune system activation, e.g., after pathogen challenge, but not in the resting immune system of non-infected fish. Current limitations to further development and implementation of immunotoxicity assays and parameters in ecotoxicological risk assessment are not primarily due to technological constraints, but are related from insufficient knowledge of (1) possible modes of action in the immune system, (2) the importance of intra- and inter-species immune system variability for the response against chemical stressors, and (3) deficits in conceptual and mechanistic assessment of combination effects of chemicals and pathogens.

PURPOSE: A comparison between suburban and rural atmospheric carbon dioxide concentrations in Northern Spain is made. METHOD: Measurements were carried out from April 2006 to November 2007 using MIR 9000 continuous analyzers based on the infrared technique. Two locations were established: a suburban site in Valladolid, a medium-sized city, and a rural location at CIBA, approximately 24 km northwest of Valladolid. RESULTS AND CONCLUSIONS: Mean suburban CO2 concentrations are 4.5 ppm higher than rural levels. Frequencies of suburban concentrations from 400 to 450 ppm were around twice the rural frequencies. The suburban daily evolution presented two maxima in the predawn hours and at 1900–2000 GMT, mainly associated to anthropogenic emissions which also affected maximum concentrations recorded in autumn–winter and minimum levels in summer. The rural variation with minimum values during the day and high levels at night is mainly related to vegetation activity which also impacts the highest CO2 concentrations obtained in spring, coinciding with maximum vegetation growth. Boundary layer processes also affected variability of concentrations recorded at both sites. Air quality at the rural site was also influenced by air mass transport from the urban plume (S, SSE, and ESE), which had a mean CO2 value of 402 ppm. By contrast, concentrations were low when SW–W and NW winds prevailed and brought cleaner air. The relationship between rural CO2 concentrations and wind speed using a mathematical fit provides a valuable estimation of the background level at the site, 384.8 ppm.

INTRODUCTION AND AIMS: The dominance of a plant species in highly metal-contaminated areas reflects its tolerance or adaptability potential to these scenarios. Hence, plants with high adaptability and/or tolerance to exceptionally high metal-contaminated scenarios may help protect environmental degradation. The present study aimed to assess the strategies adopted by common reed, Phragmites australis for its dominance in highly mercury-contaminated Ria de Aveiro coastal lagoon (Portugal). MATERIALS AND METHODS: Both plant samples and the sediments vegetated by monospecific stand of Phragmites australis were collected in five replicates from mercury-free (reference) and contaminated sites during low tide between March 2006 and January 2007. The sediments’ physico-chemical traits, plant dry mass, uptake, partitioning, and transfer of mercury were evaluated during growing season (spring, summer, autumn, and winter) of P. australis. Redox potential and pH of the sediment around roots were measured in situ using a WTW-pH 330i meter. Dried sediments were incinerated for 4 h at 500°C for the estimation of organic matter whereas plant samples were oven-dried at 60°C till constant weight for plant dry mass determination. Mercury concentrations in sediments and plant parts were determined by atomic absorption spectrometry with thermal decomposition, using an advanced mercury analyzer (LECO 254) and maintaining the accuracy and precision of the analytical methodologies. In addition, mercury bioaccumulation and translocation factors were also determined to differentiate the accumulation of mercury and its subsequent translocation to plant parts in P. australis. RESULTS AND CONCLUSIONS: P. australis root exhibited the highest mercury accumulation followed by rhizome and leaves during the reproductive phase (autumn). During the same phase, P. australis exhibited ≈5 times less mercury-translocation factor (0.03 in leaf) when compared with the highest mercury bioaccumulation factor for root (0.14). Moreover, seasonal variations differentially impacted the studied parameters. P. australis’ extraordinary ability to (a) pool the maximum mercury in its roots and rhizomes, (b) protect its leaf against mercury toxicity by adopting the mercury exclusion, and (c) adjust the rhizosphere-sediment environment during the seasonal changes significantly helps to withstand the highly mercury-contaminated Ria de Aveiro lagoon. The current study implies that P. australis has enough potential to be used for mercury stabilization and restoration of sediments/soils rich in mercury as well.

PURPOSE: Nanoscale zero valent iron (NZVI) is emerging as a new option for the treatment of contaminated soil and groundwater targeting mainly chlorinated organic contaminants (e.g., solvents, pesticides) and inorganic anions or metals. The purpose of this article is to give a short overview of the practical experience with NZVI applications in Europe and to present a comparison to the situation in the USA. Furthermore, the reasons for the difference in technology use are discussed. METHOD: The results in this article are based on an extensive literature review and structured discussions in an expert workshop with experts from Europe and the USA. The evaluation of the experiences was based on a SWOT (strength, weakness, opportunity, threat) analysis. RESULT: There are significant differences in the extent and type of technology used between NZVI applications in Europe and the USA. In Europe, only three full-scale remediations with NZVI have been carried out so far, while NZVI is an established treatment method in the USA. Bimetallic particles and emulsified NZVI, which are extensively used in the USA, have not yet been applied in Europe. Economic constraints and the precautionary attitude in Europe raise questions regarding whether NZVI is a cost-effective method for aquifer remediation. Challenges to the commercialization of NZVI include mainly non-technical aspects such as the possibility of a public backlash, the fact that the technology is largely unknown to consultants, governments and site owners as well as the lack of long-term experiences. CONCLUSION: Despite these concerns, the results of the current field applications with respect to contaminant reduction are promising, and no major adverse impacts on the environment have been reported so far. It is thus expected that these trials will contribute to promoting the technology in Europe.

Greenhouse and field studies were performed to examine the growth responses and possible phytoremediation capacity towards heavy metals of several Brassicaceae (Brassica alba, Brassica carinata, Brassica napus and Brassica nigra) and Poaceae (durum wheat and barley). Soils used featured total concentrations of Cr, Cu, Pb and Zn largely exceeding the maximum levels permitted by the Italian laws. Different organic amendments were tested such as a compost and the plant growth-promoting rhizobacterium Bacillus licheniformis. In the greenhouse experiment, plant length, leaf area index and shoots dry matter were evaluated periodically for the Brassicaceae examined. Whereas plant length, grains production, weight of 1,000 seeds, ear fertility and tiller density were determined under field conditions at the end of the crop cycle for wheat and barley. In general, the species tested appeared to be tolerant to high heavy metal concentrations in soil, and slightly significant differences were found for all parameters considered. A marked growth increase was shown to occur for Brassicaceae cultivated on compost- and bacillus-amended contaminated soils, with respect to non-amended contaminated soils. With some exception, higher growth parameters were measured for wheat and barley plants cropped from contaminated soils in comparison to non-contaminated soils. Further, bacillus amendment enhanced the length of wheat and barley plants in both non-contaminated and contaminated soils, while different effects were observed for the other parameters evaluated.

PURPOSE: The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants. METHODS: In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol–gel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV–vis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation. RESULTS: Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO2 powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity. CONCLUSION: We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.

PURPOSE: This research is on the evaluation of biosorption capability of the core of Artocarpus odoratissimus (Tarap), grown in Brunei Darussalam, towards Cd(II) and Cu(II) ions present in synthetic solutions, and to characterize the surface of Tarap particles. METHODS: Thermogravimetric analysis and surface titrations were conducted to characterize the surface of dried Tarap core particles. Atomic absorption spectroscopic measurements were conducted to determine the extent of removal of Cd(II) and Cu(II) under different experimental conditions. RESULTS: Mass reductions associated with many exothermic reaction peaks were observed beyond 200°C up to 650°C indicating the combustion of organic matter in Tarap. Dried particles of core of Tarap bear a negative surface charge promoting strong interaction towards positively charged ions, such as Cu(II) and Cd(II). Biosorption of the two metal ions on Tarap, which is relatively high beyond pH = 4, occurs within a short period of exposure time. The extent of biosorption is enhanced by acid treatment of the biosorbent, and further it does not significantly depend on the presence of nonreacting ions up to an ionic strength of 2.0 M. CONCLUSION: Strong attraction between each metal ion and the biosorbent is attributed to the negative surface charge on the biosorbent within a broad pH range. Acid treatment of the biosorbent improves sorption characteristics, suggesting that ion exchange plays an important role in the metal ion—biosorbent interaction process.