Organic matter in the bulk precipitations in Zagreb and Šibenik,Croatia

Dissolved organic carbon (DOC), surface active substances (SAS) and copper complexing capacity (CuCC) were studied in bulk precipitations collected periodically from 2003 to 2007 in the continental city of Croatia (Zagreb: n = 27) and in the city at the Adriatic coast (?ibenik: n = 38). DOC concentrations (Zagreb: 0.67–4.03 mgC/L with average concentration of 1.93 ± 0.76 mgC/L; ?ibenik: 0.44–4.13 mgC/L with average concentration of 1.83 ± 0.83 mgC/L) are similar to those measured in other samples of continental rainwater in the northern hemisphere. The concentrations of SAS in samples from Zagreb ranged from 0.055 to 0.45 eq. Triton-X-100 mg/L with average concentration of (0.14 ± 0.06) eq. Triton-X-100 mg/L. SAS fractions were of a similar range in ?ibenik (0.02–0.60 eq. Triton-X-100 mg/L) with an average concentration of 0.11 ± 0.06 eq. Triton-X-100 mg/L. However, the lowest values of SAS (between 0.02 and 0.04 eq. Triton-X-100 mg/L) were observed only in ?ibenik (27%). We have estimated that the higher pH values were responsible for lower surface activity of organic matter in bulk samples from ?ibenik. DOC may form complexes that control the transport and solubility of heavy metals in natural water. CuCC measured in ?ibenik in the range 0.066–1.4 μM Cu²⁺ was in general higher, compared to the one in Zagreb (0.010–0.586 μM Cu²⁺) which is the result of biogenically driven organic contribution to the precipitation, especially in the warmer period of the year.     

Conversion of specialised dairy farming systems into sustainable mixed farming systems in Cuba

From the 1960s onwards, a ‘High External Input’ dairy production model was applied widely in Cuba. Overall milk production of the national herd increased considerably, but the system was inefficient from both a financial and energetic point of view. In the early 1990s, after the abrupt end of inflow of capital and other resources from Eastern Europe, the dairy sector collapsed. In the short term, the modern infrastructure of milk production deteriorated and the sector experienced profound vulnerability. However, in the longer term, this situation stimulated a search for more sustainable approaches, such as low external input Mixed Farming Systems (MFS). The current study aimed to evaluate two small scale prototype farms to assess the implications of converting ‘Low External Input’ Dairy Farming Systems into MFS. Fifteen agro-ecological and financial indicators were selected and monitored over a 6-year period. Two configurations of MFS, i.e. the proportion of the farm area occupied by arable crops, were tested: 25 and 50%. Productivity, energy efficiency and cost-effectiveness all improved following conversion. Total energy input was low for both farms and decreased over time, whereas energy efficiency was high and increased over time. Human labour input was high directly following conversion, but decreased by one-third over the 6-year period. This study demonstrates, at an experimental scale, the potential of MFS to achieve ecological, productivity and financial advantages for dairy production in Cuba. Readers should send their comments on this paper to: BhaskarNath@aol.com within 3 months of publication of this issue.     

Impacts of future land use/land cover on wildfire occurrence in the Madrid region (Spain)

This paper assesses the relative importance of socioeconomic factors linked to fire occurrence through the simulation of future land use/land cover (LULC) change scenarios in the Madrid region (Spain). This region is a clear example of the socioeconomic changes that have been occurring over recent decades in the European Mediterranean as well as their impact on LULC and fire occurrence. Using the LULC changes observed between 1990 and 2006 as a reference, future scenarios were run up to 2025 with the conversion of land use and its effects model. Simultaneously, the relationship between LULC arrangement (interfaces) and historical fire occurrence was calculated using logistic regression analysis and used to quantify changes in future fire occurrence due to projected changes in LULC interfaces. The results revealed that it is possible to explain the probability of fire occurrence using only variables obtained from LULC maps, although the explanatory power of the model is low. In this context, border areas between some LULC types are of particular interest (i.e., urban/forest, grassland/forest and agricultural/forest interfaces). Results indicated that expected LULC changes in Euro-Mediterranean regions, particularly given the foreseeable increase in the wildland–urban interface, will substantially increase fire occurrence (up to 155 %). This underlines the importance of future LULC scenarios when planning fire prevention measures.     

Proximity to wood industries and respiratory symptoms in children: a sensitivity analysis

Increased prevalence of respiratory and irritation symptoms was found in children who live near a large wood industrial park. Proximity to the wood industries was used as indicator of exposure. This study describes a sensitivity analysis for the results of the survey. All the children (3-14 years) living in the area were surveyed through a parental questionnaire (n = 3854) and their addresses were geocoded. The distances from each child's home and school to the closest industry were combined, weighted and used as an indicator of exposure. A sensitivity analysis was performed to check 1) the robustness of the results to the choice of weights used for defining the exposure indicator, 2) the effect of outliers on risk estimates and 3) the sensitivity on the functional form used for modeling the dose-response function. The choice of the weights did not influence the association between proximity to the industries and respiratory symptoms. Excluding the subjects who lived far away from the industries showed that in a radius of 5 km from the industries the study did not had enough power to estimate a gradient in the dose-response function. Besides, results were sensitive to the choice of the functional form used for modeling the minimum distance. The sensitivity analyses confirmed the overall increasing trend of respiratory symptoms with proximity to the industries and pointed out that all the assumptions made for defining a proxy of exposure need to be carefully checked.     

Prioritisation of organic contaminants in a river basin using chemical analyses and bioassays

Region-specific contaminant prioritisation is an important prerequisite for sustainable and cost-effective monitoring due to the high number of different contaminants that may be present. Surface water and sediment samples from the Sava River, Croatia, were collected at four locations covering a 150-km-long river section characterised by well-defined pollution gradients. Analysis of contaminant profiles along the pollution gradients was performed by combining toxicity screening using a battery of small-scale or in vitro bioassays, which covered different modes of action, with detailed chemical characterisation based on gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). A large number of contaminants, belonging to different toxicant classes, were identified in both analysed matrices. Analyses of water samples showed that contaminants having polar character occurred in the highest concentrations, while in sediments, contributions from both non-polar and amphiphilic contaminants should be taken into account. Estimated contributions of individual contaminant classes to the overall toxicity indicated that, besides the classical pollutants, a number of emerging contaminants, including surfactants, pharmaceuticals, personal care products and plasticizers, should be taken into consideration in future monitoring activities. This work demonstrates the importance of the integrated chemical and bioanalytical approach for a systematic region-specific pollutant prioritisation. Finally, the results presented in this study confirm that hazard assessment in complex environmental matrices should be directed towards identification of key pollutants, rather than focusing on a priori selected contaminants alone.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

Influence of ozone pre-treatment on sludge anaerobic digestion: removal of pharmaceutical and personal care products

The effect of an oxidative pre-treatment with ozone on the removal of Pharmaceutical and Personal Care Products (PPCPs) during the anaerobic digestion of sewage sludge has been investigated. Besides, the digested sludge characteristics in terms of pathogens content, dewatering properties, heavy metals content and linear alkylbenzene sulfonates (LAS) were determined. During ozonation (20mg O(3)/g TSS), about 8% of volatile solids (VS) and 60% of the chemical oxygen demand (COD) were solubilized. However, no mineralization was observed. The elimination of VS and total COD during anaerobic digestion were not affected by ozone treatment with efficiencies ranging from 60% to 65%. All PPCPs considered were removed during anaerobic treatment of sludge, with efficiencies ranging from 20% to 99%. No significant influence of ozone pre-treatment was observed on PPCPs elimination except for carbamazepine. Pathogens, heavy metals and LAS contents after conventional and pre-ozonation treatment of sewage sludge were below the legal requirements. However, the dewatering properties of sludge were deteriorated when the ozone pre-treatment was applied.     

The role of citric acid in cadmium and nickel uptake and translocation, in Halimione portulacoides

Some plants have high ability to absorb heavy metals in high concentrations. In this study, Halimione portulacoides was tested in conjunction with citric acid, in order to evaluate the possible use of this plant in phytoremediation processes in salt marshes. Two different concentrations of chelator were used combined with two heavy metal concentrations. When 25microM of citric acid was applied, Cd uptake and translocation was enhanced while for Ni these processes were almost inhibited. Increasing citric acid concentration to 50microM, Ni absorption decreased by the roots while for Cd there was still an increase in root uptake. Analysing translocation with this concentration of chelator, a decreased metal content in the upper organs for both metals was observed. While for Cd an optimal concentration of 25microM of citric acid was observed for phytoremediative processes, for nickel neither concentrations of chelator showed advantages for application in this remediative method.     

Treatment of phenylmercury salts by heterogeneous photocatalysis over TiO(2)

UV/TiO(2) photocatalysis of phenylmercury salts in aqueous solutions has been performed starting from both acetate (C(6)H(5)HgCH(3)CO(2), PMA) and chloride (C(6)H(5)HgCl, PMC) salts, in the presence or the absence of oxygen at acidic pH. Removal of Hg(II) in solution took place with the simultaneous deposit of dark or pale gray solids on the photocatalyst, identified as metallic Hg (when starting from PMA) or mixtures of Hg(0) and Hg(2)Cl(2) (when starting from PMC). Partial mineralization of the organic part of both compounds has also been achieved. Hg(II) removal and mineralization were enhanced in the absence of oxygen. PMA photocatalysis followed a saturation kinetics, going from first order at low concentration to zero order at higher concentrations (>0.5mM). For PMA, reaction was faster at high pH (11) with formation of mixtures of Hg and HgO. Phenol was detected as a product of the reaction in both cases, PMA and PMC, and no formation of dangerous methyl- or ethylmercury species was observed in the first case. A mechanism for the photocatalytic reaction has been proposed. The fact that calomel was found as a deposit when starting from PMC under nitrogen suggests that the mechanism of Hg(II) transformation proceeds through successive one-electron transfer reactions passing by mercurous forms.     

Organochlorine bioaccumulation and biomarkers levels in culture and wild white seabream (Diplodus sargus)

Persistent organic pollutants (POPs), which can accumulate in the adipose fish tissues, can enter the human food chain through the consumption of fish, and cause risk to health. The use of chemical analysis, and biochemical and cellular responses is a way to detect the impact of pollutants in aquatic systems. The purpose of this study was to investigate the levels of organochlorine compounds (polychlorinated biphenyls - PCB and p,p'-dichlorodiphenyltrichloroethane and its metabolites - tDDT) in, wild and cultivated, white seabream (Diplodus sargus), and also its biological effects that were evaluated by assessing the activity of biotransformation enzymes and genotoxic effects. To achieve that we have sampled five different size classes (I - 13 g, II - 64 g, III - 143 g, IV - 315 g and V - 441 g) of white seabream from a local aquaculture, and also a group of wild fish (375g) in order to compare accumulation and responses between cultured and wild fish. White seabream, cultured and wild, presented low levels of organochlorine content, both in liver and in muscle. Wild white seabream, in comparison to cultured ones at the marketable size, showed lower organochlorine accumulation. Biotransformation enzymes showed negative correlations with organochlorine levels in liver. Micronucleous numbers revealed that wild white seabream are not so exposed to genotoxic compounds as cultured ones.