Source term characterisation using concentration trends and geochemical associations of Pb and Zn in river sediments in the vicinity of a disused mine site: Implications for contaminant metal dispersion processes

River sediment at a disused lead-zinc mine was analysed to provide an understanding of the chemical nature of the source term for contaminated sediment exported from the site. Changes in concentration and geochemical associations of Pb and Zn were measured using aqua regia digestion and the BCR sequential extraction procedure. Sediment in the immediate vicinity of the mine was highly contaminated with Pb (max. c. 11,000 mg kg⁻¹) and Zn (max. c. 30,000 mg kg⁻¹), but these values declined rapidly within 1 km of the mine due to dilution and hydraulic sorting. Lead fractionation changed from being predominantly in the reducible fraction to being in the acetic acid-extractable fraction, whereas Zn was predominantly in the residual fraction. This material is transported as fine sediment in the river system.     

Diagnosis of dissolved organic matter removal by GAC treatment in biologically treated papermill effluents using advanced organic characterisation techniques

Granular activated carbon (GAC) exhaustion rates on pulp and paper effluent from South East Australia were found to be a factor of three higher (3.62 cf. 1.47 kg m⁻³) on Kraft mills compared to mills using Thermomechanical pulping supplemented by Recycled Fibre (TMP/RCF). Biological waste treatment at both mills resulted in a final effluent COD of 240 mg L⁻¹. The dissolved organic carbon (DOC) was only 1.2 times higher in the Kraft effluent (70 vs. 58 mg L⁻¹), however, GAC treatment of Kraft and TMP/RCF effluent was largely different on the DOC persisted after biological treatment. The molecular mass (636 vs. 534 g mol⁻¹) and aromaticity (5.35 vs. 4.67 L mg⁻¹ m⁻¹) of humic substances (HS) were slightly higher in the Kraft effluent. The HS aromaticity was decreased by a factor of 1.0 L mg⁻¹ m⁻¹ in both Kraft and TMP/RCF effluent. The molecular mass of the Kraft effluent increased by 50 g mol⁻¹ while the molecular mass of the TMP/RCF effluent was essentially unchanged after GAC treatment; the DOC removal efficiency of the GAC on Kraft effluent was biased towards the low molecular weight humic compounds. The rapid adsorption of this fraction, coupled with the slightly higher aromaticity of the humic components resulted in early breakthrough on the Kraft effluent. Fluorescence excitation-emission matrix analysis of the each GAC treated effluent indicated that the refractory components were higher molecular weight humics on the Kraft effluent and protein-like compounds on the TMP/RCF effluent. Although the GAC exhaustion rates are too high for an effective DOC removal option for biologically treated pulp and paper mill effluents, the study indicates that advanced organic characterisation techniques can be used to diagnose GAC performance on complex effluents with comparable bulk DOC and COD loads.     

Rapid quantification of polycyclic aromatic hydrocarbons in hydroxypropyl-beta-cyclodextrin (HPCD) soil extracts by synchronous fluorescence spectroscopy (SFS)

Synchronous fluorescence spectroscopy (SFS) was directly applied to rapidly quantify selected polycyclic aromatic hydrocarbons (PAHs: benzo[a]pyrene and pyrene) in aqueous hydroxypropyl-beta-cyclodextrin (HPCD) soil extract solutions from a variety of aged contaminated soils containing four different PAHs. The method was optimized and validated. The results show that SFS can be used to analyse benzo[a]pyrene and pyrene in HPCD based soil extracts with high sensitivity and selectivity. The linear calibration ranges were 4.0x10(-6)-1.0x10(-3)mM for benzo[a]pyrene and 6.0x10(-6)-1.2x10(-3)mM for pyrene in 10mM HPCD aqueous solution alone. The detection limits according to the error propagation theory for benzo[a]pyrene and pyrene were 3.9x10(-6) and 5.4x10(-6)mM, respectively. A good agreement between SFS and HPLC was reached for both determinations of PAHs in HPCD alone and in soil HPCD extracts. Hence, SFS is a potential means to simplify the present non-exhaustive hydroxypropyl-beta-cyclodextrin (HPCD)-based extraction technique for the evaluation of PAH bioavailability in soil.     

Dietary antioxidants (selenium and N-acetylcysteine) modulate paraoxonase 1 (PON1) in PCB 126-exposed rats

Environmental pollutants polychlorinated biphenyls (PCBs), especially dioxin-like PCBs, cause oxidative stress and associated toxic effects, including cancer and possibly atherosclerosis. We previously reported that PCB 126, the most potent dioxin-like PCB congener, not only decreases antioxidants such as hepatic selenium (Se), Se-dependent glutathione peroxidase, and glutathione (GSH) but also increases levels of the antiatherosclerosis enzyme paraoxonase 1 (PON1) in liver and serum. To probe the interconnection of these three antioxidant systems, Se, GSH, and PON1, we examined the influence of varying levels of dietary Se and N-acetylcysteine (NAC), a scavenger of reactive oxygen species (ROS) and precursor for GSH synthesis, on PON1 in the absence and presence of PCB 126 exposure. Male Sprague–Dawley rats, fed diets with differing Se levels (0.02, 0.2, or 2 ppm) or NAC (1 %), were treated with a single intraperitoneal injection of corn oil or various doses of PCB 126 and euthanized 2 weeks later. PCB 126 significantly increased liver PON1 mRNA, protein level and activity, and serum PON1 activity in all dietary groups but did not consistently increase thiobarbituric acid levels (thiobarbituric acid reactive substances, TBARS), an indicator of lipid oxidation and oxidative stress, in liver or serum. Inadequate (high or low) dietary Se decreased baseline and PCB 126-induced aryl hydrocarbon receptor (AhR) expression but further increased PCB 126-induced cytochrome P450 1A1 (CYP1A1) expression, the enzyme believed to be the cause for PCB 126-induced oxidative stress. In addition, a significant inverse relationship was observed not only between dietary Se levels and PON1 mRNA and PON1 activity but also with TBARS levels in the liver, suggesting significant antioxidant protection from dietary Se. NAC lowered serum baseline TBARS levels in controls and increased serum PON1 activity but lowered liver PON1 activities in animals treated with 1 μmol/kg PCB 126, suggesting antioxidant activity by NAC primarily in serum. These results also show an unexpected predominantly inverse relationship between Se or NAC and PON1 during control and PCB 126 exposure conditions. These interactions should be further explored in the development of dietary protection regimens.     

Mercury in the Mediterranean. Part 2: processes and mass balance

Mass balance of contaminants can provide useful information on the processes that influence their concentrations in various environmental compartments. The most important sources, sinks and the equilibrium or non-equilibrium state of the contaminant in individual environmental compartments can also be identified. Using the latest mercury speciation data, the results of numerical models and the results of recent studies on mercury transport and transformation processes in the marine environment, we have re-evaluated the total mercury (HgT) mass balance in the Mediterranean Sea. New calculations have been performed employing three distinct marine layers: the surface layer, the thermocline and the deep sea. New transport mechanisms, deep water formation and density-driven sinking and upwelling, were included in the mass balance calculations. The most recent data have even enabled the calculation of an approximate methylmercury (MeHg) mass balance. HgT is well balanced in the entire Mediterranean, and the discrepancies between inputs and outputs in individual layers do not exceed 20 %. The MeHg balance shows larger discrepancies between gains and losses due to measurement uncertainties and gaps in our knowledge of Hg species transformation processes. Nonetheless, the main sources and sinks of HgT (deposition and evasion) and MeHg (fluxes from sediment, outflow through the Gibraltar Strait) are in accordance with previous studies on mercury in the Mediterranean Basin. Mercury in the Mediterranean fish harvest is the second largest MeHg sink; about 300 kg of this toxic substance is consumed annually with sea food.     

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model’s ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year^?1 of elemental Hg.     

Edible Protein Energy Return on Investment Ratio (ep-EROI) for Spanish Seafood Products

Life cycle assessment (LCA) has developed into a useful methodology to assess energy consumption of fishing fleets and their derived seafood products, as well as the associated environmental burdens. In this study, however, the life cycle inventory data is used to provide a dimensionless ratio between energy inputs and the energy provided by the fish: the edible protein energy return on investment (ep-EROI). The main objective was to perform a critical comparison of seafood products landed in Galicia (NW Spain) in terms of ep-EROI. The combination of energy return on investment (EROI) with LCA, the latter having standardized mechanisms regarding data acquisition and system boundary delimitation, allowed a reduction of uncertainties in EROI estimations. Results allow a deeper understanding of the energy efficiency in the Galician fishing sector, showing that small pelagic species present the highest ep-EROI values if captured using specific fishing techniques. Finally, results are expected to provide useful guidelines for policy support in the EU’s Common Fisheries Policy.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-013-0426-2) contains supplementary material, which is available to authorized users.     

Public perception of odour and environmental pollution attributed to MSW treatment and disposal facilities: A case study

If residents’ perceptions, concerns and attitudes towards waste management facilities are either not well understood or underestimated, people can produce strong opposition that may include protest demonstrations and violent conflicts such as those experienced in the Campania Region of Italy. The aim of this study was to verify the effects of the closure of solid waste treatment and disposal facilities (two landfills and one RDF production plant) on public perception of odour and environmental pollution. The study took place in four villages in Southern Italy. Identical questionnaires were administered to residents during 2003 and after the closure of the facilities occurred in 2008. The residents’ perception of odour nuisance considerably diminished between 2003 and 2009 for the nearest villages, with odour perception showing an association with distance from the facilities. Post closure, residents had difficulty in identifying the type of smell due to the decrease in odour level. During both surveys, older residents reported most concern about the potentially adverse health impacts of long-term exposure to odours from MSW facilities. However, although awareness of MSW facilities and concern about potentially adverse health impacts varied according to the characteristics of residents in 2003, substantial media coverage produced an equalisation effect and increased knowledge about the type of facilities and how they operated. It is possible that residents of the village nearest to the facilities reported lower awareness of and concern about odour and environmental pollution because the municipality received economic compensation for their presence.     

The Use of Indoor Air Measurements To Evaluate Intrusion of Subsurface VOC Vapors into Buildings

ABSTRACT

The implementation of a risk-based corrective action approach often requires consideration of soil vapor migration into buildings and potential inhalation exposure and risk to human health. Due to the uncertainty associated with models for this pathway, there may be a desire to analyze indoor air samples to validate model predictions, and this approach is followed on a somewhat frequent basis at sites where risks are considered potentially significant. Indoor air testing can be problematic for a number of reasons. Soil vapor intrusion into buildings is complex, highly dependent on site-specific conditions, and may vary over time, complicating the interpretation of indoor air measurements when the goal is to deduce the subsurface-derived component. An extensive survey of indoor air quality data sets highlights the variability in indoor volatile organic compound (VOC) concentrations and numerous sources that can lead to elevated VOC levels. The contribution from soil vapor is likely to be small relative to VOCs from other sources for most sites. In light of these challenges, we discuss how studies that use indoor air testing to assess subsurface risks could be improved. To provide added perspective, we conclude by comparing indoor air concentrations and risks arising from subsurface VOCs, predicted using standard model equations for soil vapor fate and intrusion into buildings, to those associated with indoor sources.     

The Silver Valley Lead Study:The Relationship between Childhood Blood Lead Levels and Environmental Exposure

This paper is directed to those persons concerned with the relationship between blood lead levels and environmental exposures to lead. Information presented in this paper represents one of the largest collections of epidemiologica! data relating blood lead levels to environmental exposures. The observed annual average ambient air lead concentration ranged from approximately 0.5 ng Pb/m³ to 23 ng Pb/m³, while lead in soil ranged from 50-24,600 ppm. Blood lead levels of children (ages 1-9 years) are related to a host of environmental variables via regression techniques. Blood lead levels were found to be most influenced by five variables. These variables are: ambient air lead, soil lead, age of the child, dustiness of the home, and occupational status of the parents. It is concluded, based upon the results of this study, that any environmental control strategy should address both the air and the soil. Soil levels in excess of 1000 ppm lead as well as air lead levels greater than 2 jug Pb/m³, 30 day average, were found to be unacceptable.