Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Foliar response of an Ailanthus altissima clone in two sites with different levels of ozone-pollution

Potted plants of Ailanthus altissima, produced by root suckers coming from a single symptomatic mother tree, were placed in two sites in the vicinity of Florence (central Italy), with different levels of ozone pollution. These plants were kept in well watered conditions during the period May-September 1999. In the high pollution site (Settignano-SET) the level of ozone exposure (AOT40) reached at the end of the season a value of 31 ppm h, whereas in the "low pollution" site (Cascine-CAS) the exposure to ozone was 11 ppm h. A. altissima showed foliar symptoms in early July at SET and in the second half of July at CAS when exposure values reached 5 ppm h at both sites. However, at the end of August the conditions of the plantlets were rather similar in both sites. Microscopic and ultrastructural analysis were performed at the first onset of symptoms at SET (the CAS leaflets were asymptomatic). Observing the upper leaf surface where the brown stipples were visible, it was found that the cells of the palisade mesophyll displayed loss of chlorophyll and the organelles in the cytoplasm were damaged. Swelling of thylacoids was observed in the CAS leaflets, thus indicating the possible onset of a pre-visual damage. The injured cells were separated from the healthy ones by a layer of callose. We conclude that the sensitivity to ozone of A. altissima leaves is related to its leaf structure, with low leaf density and large intercellular spaces. Cell walls, as well as acting as mechanical barriers against the spread of ozone within the cell, also provide important detoxifying processes.     

Biomonitoring of urinary metals in athletes according to particulate matter air pollution before and after exercise

Environmental Science and Pollution Research - Exposure to air pollution during physical exercise is a health issue because fine particulate matter (dimension < 10 μm; PM10) includes...     

Illicit psychotropic substance contents in the air of Italy

Two in-field campaigns were performed in 2009 to elucidate the contents of illicit psychotropic substances in airborne particulates of Italian cities. Twenty-eight localities of eight Italian regions were investigated in winter, and further eleven sites in June (14 regions in total), thanks to contribution of Regional Environmental Agencies. Cocaine was found almost everywhere, although some sites were rural or suburban. The maximum was recorded in Milan in winter (～0.39 ng m^?3), and “high” values (up to ～0.16 ng m^?3) in other Northern cities and in Rome. Besides cocaine, three cannabinoids will be monitored, namely Δ⁹-tetrahydrocannabinol, cannabidiol and cannabinol. The three compounds often affected the air at lower extents than cocaine, and sometimes resulted absent. Cannabinol accounted for up to 90% of the total. The concentrations of illicit compounds were up to six times lower in June than in winter. This decrease was probably induced by the lowering of boundary layer height typical of winter, and by the oxidizing capacity of atmosphere, which is stronger in the warm season. Compared to n-alkanes, polynuclear aromatic compounds, nicotine, caffeine and airborne particulate, cocaine seemed to follow a peculiar behaviour; in fact, meaningful (≥0.80) Pearson (linear) regression coefficients were calculated from the corresponding concentrations only at local scale (e.g. Rome), and within just one season. Improvements of the method are needed to monitor illicit drug metabolites (e.g. benzoylecgonine, ecgonine methyl ester, 9-carboxy-11-nor-Δ⁹-tetrahydrocannabinol), heroin and semi-volatile amphetamines.     

The adaptive response of lichens to mercury exposure involves changes in the photosynthetic machinery

Lichens are an excellent model to study the bioaccumulation of heavy metals but limited information is available on the molecular mechanisms occurring during bioaccumulation. We investigated the changes of the lichen proteome during exposure to constant concentrations of mercury. We found that most of changes involves proteins of the photosynthetic pathway, such as the chloroplastic photosystem I reaction center subunit II, the oxygen-evolving protein and the chloroplastic ATP synthase β-subunit. This suggests that photosynthesis is a target of the toxic effects of mercury. These findings are also supported by changes in the content of photosynthetic pigments (chlorophyll a and b, and β-carotene). Alterations to the photosynthetic machinery also reflect on the structure of thylakoid membranes of algal cells. Response of lichens to mercury also involves stress-related proteins (such as Hsp70) but not cytoskeletal proteins. Results suggest that lichens adapt to mercury exposure by changing the metabolic production of energy.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Maintaining the Conservation Value of Shifting Cultivation Landscapes Requires Spatially Explicit Interventions

Fallow vegetation within landscapes dominated by shifting cultivation represents a woody species pool of critical importance with considerable potential for biodiversity conservation. Here, through the analysis of factors that influence the early stages of fallow vegetation regrowth in two contrasting forest margin landscapes in Southern Cameroon, we assessed the impact of current trends of land use intensification and expansion of the cultivated areas, upon the conservation potential of shifting cultivation landscapes. We combined the analysis of plot and landscape scale factors and identified a complex set of variables that influence fallow regrowth processes in particular the characteristics of the agricultural matrix and the distance from forest. Overall we observed a decline in the fallow species pool, with composition becoming increasingly dominated by species adapted to recurrent disturbance. It is clear that without intervention and if present intensification trends continue, the potential of fallow vegetation to contribute to biodiversity conservation declines because of a reduced capacity, (1) to recover forest vegetation with anything like its original species composition, (2) to connect less disturbed forest patches for forest dependent organisms. Strategies to combat biodiversity loss, including promotion of agroforestry practices and the increase of old secondary forest cover, will need not only to operate at a landscape scale but also to be spatially explicit, reflecting the spatial pattern of species reservoirs and dispersal strategies and human usage across landscapes.     

Electroassisted methods for waste destruction: silver(II) and peroxydisulfate reagents in the electrochemically mediated oxidation of polyaromatic sulfonates

The electrochemical oxidation is a promising process for organic pollutants which are recalcitrant to biological degradation. The anodic oxidation of 1,5-naphthalenedisulfonic acid, hereafter NDS, was evaluated at a Pt anode using in situ generated Ag(II) cation or peroxydisulfate [S2O(8)(2-)] anion as mediators. Kinetics of the direct chemical oxidation of NDS in the presence of Na2S2O8, and the identification of some oxidation intermediates are also reported. An analysis of the results shows that Ag(II) is characterized by a high-reaction rates, while [S2O(8)(2-)] performs the oxidation of NDS in a complete way.     

Assessing strategies to mitigate phosphorus leaching from drained clay soils

Assessing mitigation of phosphorus (P) leaching from subsurface drainage systems is challenging due to high spatial and temporal variation in leaching. Mean measured total P leaching from a clayey soil in an eight-year study period (four replicates per treatment) was (kg ha^?1 year^?1): 1.21 from shallow autumn tillage (ShT), 0.84 from unfertilised fallow (UF), 0.81 from conventional autumn ploughing (CT) and 0.57 from structure liming (SL–CT). Treatment was not significant using Richards–Baker flow index or a distance factor as covariate (p = 0.084 and 0.057). A tendency for lower leaching was obtained comparing SL-CT with ShT (p _adjusted = 0.060 and 0.009 respectively). A combination of measures adapted to drainage conditions and clay content in different parts of the field is proposed since P leaching was approximately halved from an adjacent field (4.3 ha) in a three-year post-period compared with a three-year pre-period for structure liming the entire field and drainage system renovation plus structure lime drain backfilling.     

Occurrence of spruce bark beetles in forest stands at different levels of air pollution stress

The spruce bark beetle, Ips typographus (L.) is the most serious pest of mature spruce stands, mainly Norway spruce, Picea abies (L.) Karst. throughout Eurasia. A complex of weather-related events and other environmental stresses are reported to predispose spruce stands to bark beetle attack and subsequent tree mortality; however the possible role of industrial pollution as a predisposing factor to attack by this species is poorly understood. The abundance and dynamics of I. typographus populations was evaluated in 60-80 year old Norway spruce stands occurring on 10 x 50 ha sites in five countries within the Carpathian range that were selected in proximity to established ozone measurement sites. Data were recorded on several parameters including the volume of infested trees, captures of adult beetles in pheromone traps, number of attacks, and the presence and relative abundance of associated bark beetle species. In several cases, stands adjacent to sites with higher ozone values were associated with higher bark beetle populations. The volume of sanitary cuttings, a reflection of tree mortality, and the mean daily capture of beetles in pheromone traps were significantly higher at sites where the O(3) level was higher. However, the mean infestation density on trees was higher in plots associated with lower O(3) levels. Captures of beetles in pheromone traps and infestation densities were higher in the zone above 800 m. However, none of the relationships was conclusive, suggesting that spruce bark beetle dynamics are driven by a complex interaction of biotic and abiotic factors and not by a single parameter such as air pollution.