Predicting dioxin-like PCBs soil contamination levels using milk of grazing animal as indicator

Dioxin-like PCBs (dl-PCBs) are ubiquitous persistent organic pollutants of recognized negative effects on human health. Assessing highly polluted areas should be an important public health issue. This study proposes to use the milk of grazing animals as a bioindicator of dl-PCB contamination in the environment. The hypothesis is that milk concentration of dl-PCBs are related to soil concentrations of these compounds, and that soils are generally reflective of a larger environmental issue of dl-PCB contamination. In this study, we evaluate the possibility of predicting soil concentrations using milk of sheep, cows and buffalos in a spatial model. For this purpose, samples of soil and milk collected in Campania (Italy) were introduced in a GIS platform to perform geostatistical analysis for building a simple predictive model. The ordinary least squares regressions (OLS) showed a statistically significant correlation (p < 0.05) between soil and milk contamination. However, this relationship was spatially variable. Thus, a geographically weighted regression (GWR) was performed, obtaining R² values of 0.91, 0.77 and 0.66 for sheep’s, buffalo’s and cow’s milk respectively. Assessed the mathematical relationships between the variables, new data was introduced to evaluate the performance of the model. Predictions of soil contamination with dl-PCBs using sheep’s, cow’s and buffalo’s milk showed a mean error of 23%, 25% and 36% respectively. According to these results the sheep’s milk can be considered the best bioindicator of dl-PCBs contamination among the three species. The results of this project evidence the potentialities of the proposed approach to assess bioindicator performance in a spatial predictive model.     

The assessment of particulate matter emitted from stone-crushing industry by correlating rock textures with particles generated after comminution and dispersed in air environment

The generation and emission of particulate matter from abrasion industry are subjects of the pollution monitoring by multidisciplinary study involving earth sciences and engineering disciplines. This work investigates the correlation between textural properties of in situ rock with class size distribution and morphology of particles generated after rock comminution and particles emitted in the air. A special comminution-dust sampling architecture was realised. The combined use of scanning electron microscopy and particle size analyser was considered in performing digital image analysis on both crushed products and airborne particles collected onto membrane filters. The results show that the size and morphology of crushed particles are linked to the petrographic rock properties. In particular, particles with fibrous morphology are prominent in rocks showing foliated textures where elongated minerals occurred, with implication for asbestos-bearing rocks. For what concerns the airborne particles, the results show that their aerodynamic diameters are independent of the crusher operating conditions. External parameters probably intervene in the distribution of the airborne particles emission, including the dynamic air fluxes, or environmental conditions. By applying mathematical models, the morphology and size range of airborne particles following the comminution processes can be predicted, and results has implication for pollutants contamination due to particulate matters emitted by crush stone industry.     

Acceptable Cancer Risks: Probabilities and Beyond

The acceptability of cancer risk requires consideration of factors that extend beyond mere numerical representations, such as either individual lifetime risk in excess of background and excess incidence. Recently, use of these numbers has been tempered by the addition of qualitative weights-of-evidence that describe the degree of support provided by animal and epidemiologic results. Nevertheless, many other factors, most of which are not quantitative, require incorporation but remain neglected by the analyst eager to use quantitative results.

In this paper we show that simple risk measures are often fraught with problems. Moreover, these measures do not incorporate the very essence of acceptability, which includes notions of responsibility, accountability, equity, and procedural legitimacy, among others. We link the process of risk assessment to those legal and regulatory standards that shape it. These standards are among the principal means to resolve risk-related disputes and to enhance the balancing of competing interests when science and law meet on uncertain and often conjectural ground.

We conclude the paper with a proposal for the portfolio approach to manage cancer risks and to deal with uncertain scientific information. This approach leads to the concept of "provisional acceptability," which reflects the choices available to the decisionmaker, and the trade-offs inherent to such choices.     

Use of a reactive transport model to describe reductive dechlorination (RD) as a remediation design tool: application at a CAH-contaminated site

In this paper, a numerical model is presented that is capable of describing the complex set of biochemical processes that occur in chlorinated aliphatic hydrocarbon (CAH)-contaminated groundwater when an exogenous electron donor is added. The reactive pattern is based on the degradation pathways of both chlorinated ethanes and ethenes, and it includes electron donor production (H₂ and acetate) from the fermentation of an organic substrate as well as rate-limiting processes related to electron acceptor competition. Coupling of the kinetic model to a convection–dispersion module is described. The calibration phase was carried out using data obtained at a real CAH-contaminated site in the north of Italy. Model simulations of different application scenarios are presented to draw general conclusions on the effectiveness of reductive dechlorination (RD) as a possible cleanup strategy. Early outcomes indicate that cleanup targets can only be achieved if source longevity is reduced. Therefore, metabolic RD is expected to produce beneficial effects because it is known to induce bioenhanced degradation and transformation of CAHs.     

Spatial distribution and partitioning of polychlorinated biphenyl and organochlorine pesticide in water and sediment from Sarno River and Estuary,Southern Italy

The Sarno River is nicknamed “the most polluted river in Europe”. The main goal of this study is to enhance our knowledge on the Sarno River water and sediment quality and on its environmental impact on the gulf of Naples (Tyrrhenian Sea, Central Mediterranean Sea) in order to become a useful assessment tool for the regional administrations. For these reasons, 32 selected polychlorinated biphenyls (PCBs) and aldrin, α-BHC, β-BHC, δ-BHC, γ-BHC (lindane), 4,4′-DDD, 4,4′-DDE, 4,4′-DDT, dieldrin, endosulfan I, endosulfan II, endosulfan sulphate, endrin, endrin aldehyde, heptachlor, heptachlor epoxide (isomer B) and methoxychlor were determined in the water dissolved phase (DP), suspended particulate matter (SPM) and sediments. Total concentrations of PCBs ranged from 1.4 to 24.9 ng L^?1 in water (sum of DP and SPM) and from 1.01 to 42.54 ng g^?1 in sediment samples. The concentrations of total organochlorine pesticides (OCPs) obtained in water (sum of DP and SPM) ranged from 0.54 to 7.32 ng L^?1 and from 0.08 to 5.99 ng g^?1 in sediment samples. Contaminant discharges of PCBs and OCPs into the sea were calculated in about 1,247 g day^?1 (948 g day^?1 of PCBs and 326 g day^?1 of OCPs), showing that this river should account as one of the main contribution sources of PCBs and OCPs to the Tyrrhenian Sea.     

Assessment of nitrous oxide emission from cement plants: Real data measured with both Fourier transform infrared and nondispersive infrared techniques

Nitrous oxide (N₂O) is the third most important greenhouse gas after carbon dioxide and methane, and contributes about 6% to the greenhouse effect. Nitrous oxide is a minor component of the atmosphere, and it is a thousand times less than carbon dioxide (CO₂). Nevertheless, it is much more potent than CO₂ and methane, owing to its long stay in the atmosphere of approximately 120 yr and the high global warming potential (GWP) of 298 times that of CO₂. Although greenhouse gases are natural in the atmosphere, human activities have changed the atmospheric concentrations. Most of the values of emission of nitrous oxide are still obtained by means of emission factors and not actually measured; the lack of real data may result in an underestimation of current emissions. The emission factors used for the calculation of N₂O can be obtained from the “Guidelines for the implementation of the national inventory of emissions” of the Intergovernmental Panel on Climate Change, which refer to all nations for the realization of their inventory. This study will present real data, measured in several Italian cement plants with different characteristics. The work also shows a comparison between N₂O concentration measured with in situ Fourier transform IR (FTIR) and the reference method EN ISO 21258 based on nondispersive IR (NDIR), in order to investigate the interfering compounds in the measurement with NDIR.

Implications:N₂O may arise as an unwanted by-product of nitrogen oxide (NO_x) abatement systems, in particular selective noncatalytic reduction (SNCR). Since it is applied in the cement plants, N₂O emission from cement industry is evaluated, with both FTIR and NDIR instrument. Several considerations emerged from the results. First of all, the emission from this industrial sector is not negligible, and for that reason N₂O concentration should be regulated; another observation is that the reference method based on the NDIR technique is not as selective as FTIR could be.     

Integrated Ambient and Microenvironment Model for Estimation of PM10 Exposures of Children in Annual and Episode Settings

Particulate matter air pollution is estimated to cause in the order of 350,000 excess deaths in the European Union calling for policy development and evaluation tools. In the current work, a model for PM₁₀ exposures of children is developed using microenvironment time activities and infiltration of ambient pollution indoors, both evaluated against observations earlier and integrated with city-wide air quality models in the current work. The model is demonstrated using data from two cities in Italy. High-end short-term exposures are characterized by an episode-day situation in Turin, and annual mean exposures in downtown Bologna. The air quality model was unable to capture the highest levels during the episode, and therefore, the exposure model was adjusted using observed–modeled ratio from a monitoring station. Air quality model performance for the annual levels was significantly better. Annual exposure variability within the target population was 1.5-fold in the downtown area Bologna and tenfold during the episode day in Turin.     

Spatial scales of variation in lichens: implications for sampling design in biomonitoring surveys

The variability of biological data is a main constraint affecting the quality and reliability of lichen biomonitoring surveys for estimation of the effects of atmospheric pollution. Although most epiphytic lichen bioindication surveys focus on between-site differences at the landscape level, associated with the large scale effects of atmospheric pollution, current protocols are based on multilevel sampling, thus adding further sources of variation and affecting the error budget. We test the hypothesis that assemblages of lichen communities vary at each spatial scale examined, in order to determine what scales should be included in future monitoring studies. We compared four sites in Italy, along gradients of atmospheric pollution and climate, to test the partitioning of the variance components of lichen diversity across spatial scales (from trunks to landscapes). Despite environmental heterogeneity, we observed comparable spatial variance. However, residuals often overcame between-plot variability, leading to biased estimation of atmospheric pollution effects.     

Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.