A review of exposure assessment methods for epidemiological studies of health effects related to industrially contaminated sites.

BACKGROUND: this paper is based upon work from COST Action ICSHNet. Health risks related to living close to industrially contaminated sites (ICSs) are a public concern. Toxicology-based risk assessment of single contaminants is the main approach to assess health risks, but epidemiological studies which investigate the relationships between exposure and health directly in the affected population have contributed important evidence. Limitations in exposure assessment have substantially contributed to uncertainty about associations found in epidemiological studies. OBJECTIVES: to examine exposure assessment methods that have been used in epidemiological studies on ICSs and to provide recommendations for improved exposure assessment in epidemiological studies by comparing exposure assessment methods in epidemiological studies and risk assessments. METHODS: after defining the multi-media framework of exposure related to ICSs, we discussed selected multi-media models applied in Europe. We provided an overview of exposure assessment in 54 epidemiological studies from a systematic review of hazardous waste sites; a systematic review of 41 epidemiological studies on incinerators and 52 additional studies on ICSs and health identified for this review. RESULTS: we identified 10 multi-media models used in Europe primarily for risk assessment. Recent models incorporated estimation of internal biomarker levels. Predictions of the models differ particularly for the routes 'indoor air inhalation' and 'vegetable consumption'. Virtually all of the 54 hazardous waste studies used proximity indicators of exposure, based on municipality or zip code of residence (28 studies) or distance to a contaminated site (25 studies). One study used human biomonitoring. In virtually all epidemiological studies, actual land use was ignored. In the 52 additional studies on contaminated sites, proximity indicators were applied in 39 studies, air pollution dispersion modelling in 6 studies, and human biomonitoring in 9 studies. Exposure assessment in epidemiological studies on incinerators included indicators (presence of source in municipality and distance to the incinerator) and air dispersion modelling. Environmental multi-media modelling methods were not applied in any of the three groups of studies. CONCLUSIONS: recommendations for refined exposure assessment in epidemiological studies included the use of more sophisticated exposure metrics instead of simple proximity indicators where feasible, as distance from a source results in misclassification of exposure as it ignores key determinants of environmental fate and transport, source characteristics, land use, and human consumption behaviour. More validation studies using personal exposure or human biomonitoring are needed to assess misclassification of exposure. Exposure assessment should take more advantage of the detailed multi-media exposure assessment procedures developed for risk assessment. The use of indicators can be substantially improved by linking definition of zones of exposure to existing knowledge of extent of dispersion. Studies should incorporate more often land use and individual behaviour.

Opportunities and challenges in the use of coal fly ash for soil improvements--a review.

Coal fly ash (CFA), a by-product of coal combustion has been regarded as a problematic solid waste, mainly due to its potentially toxic trace elements, PTEs (e.g. Cd, Cr, Ni, Pb) and organic compounds (e.g. PCBs, PAHs) content. However, CFA is a useful source of essential plant nutrients (e.g. Ca, Mg, K, P, S, B, Fe, Cu and Zn). Uncontrolled land disposal of CFA is likely to cause undesirable changes in soil conditions, including contamination with PTEs, PAHs and PCBs. Prudent CFA land application offers considerable opportunities, particularly for nutrient supplementation, pH correction and ameliorating soil physical conditions (soil compaction, water retention and drainage). Since CFA contains little or no N and organic carbon, and CFA-borne P is not readily plant available, a mixture of CFA and manure or sewage sludge (SS) is better suited than CFA alone. Additionally, land application of such a mixture can mitigate the mobility of SS-borne PTEs, which is known to increase following cessation of SS application. Research analysis further shows that application of alkaline CFA with or without other amendments can help remediate at least marginally metal contaminated soils by immobilisation of mobile metal forms. CFA land application with SS or other source of organic carbon, N and P can help effectively reclaim/restore mining-affected lands. Given the variability in the nature and composition of CFA (pH, macro- and micro-nutrients) and that of soil (pH, texture and fertility), the choice of CFA (acidic or alkaline and its application rate) needs to consider the properties and problems of the soil. CFA can also be used as a low cost sorbent for the removal of organic and inorganic contaminants from wastewater streams; the disposal of spent CFA however can pose further challenges. Problems in CFA use as a soil amendment occur when it results in undesirable change in soil pH, imbalance in nutrient supply, boron toxicity in plants, excess supply of sulphate and PTEs. These problems, however, are usually associated with excess or inappropriate CFA applications. The levels of PAHs and PCBs in CFA are generally low; their effects on soil biota, uptake by plants and soil persistence, however, need to be assessed. In spite of this, co-application of CFA with manure or SS to land enhances its effectiveness in soil improvements.

Functional Trait Variation Among and Within Species and Plant Functional Types in Mountainous Mediterranean Forests.

Plant structural and biochemical traits are frequently used to characterise the life history of plants. Although some common patterns of trait covariation have been identified, recent studies suggest these patterns of covariation may differ with growing location and/or plant functional type (PFT). Mediterranean forest tree/shrub species are often divided into three PFTs based on their leaf habit and form, being classified as either needleleaf evergreen (Ne), broadleaf evergreen (Be), or broadleaf deciduous (Bd). Working across 61 mountainous Mediterranean forest sites of contrasting climate and soil type, we sampled and analysed 626 individuals in order to evaluate differences in key foliage trait covariation as modulated by growing conditions both within and between the Ne, Be, and Bd functional types. We found significant differences between PFTs for most traits. When considered across PFTs and by ignoring intraspecific variation, three independent functional dimensions supporting the Leaf-Height-Seed framework were identified. Some traits illustrated a common scaling relationship across and within PFTs, but others scaled differently when considered across PFTs or even within PFTs. For most traits much of the observed variation was attributable to PFT identity and not to growing location, although for some traits there was a strong environmental component and considerable intraspecific and residual variation. Nevertheless, environmental conditions as related to water availability during the dry season and to a smaller extend to soil nutrient status and soil texture, clearly influenced trait values. When compared across species, about half of the trait-environment relationships were species-specific. Our study highlights the importance of the ecological scale within which trait covariation is considered and suggests that at regional to local scales, common trait-by-trait scaling relationships should be treated with caution. PFT definitions by themselves can potentially be an important predictor variable when inferring one trait from another. These findings have important implications for local scale dynamic vegetation models.

Monometal and competitive adsorption of heavy metals by sewage sludge-amended soil.

Sewage sludge-amended soils may alter their ability to adsorb heavy metals over time, due to the decomposition of sludge-borne organic matter. Thus, we studied Cd, Ni, and Zn adsorption by a sewage sludge-amended soil (Typic Xerofluvent) before and after one-year incubation in both monometal and competitive systems. In the monometal system, the order of decreasing sorption was Zn>Cd>Ni. Competition significantly reduced metal K(d), especially that of Cd which decreased by nearly 50%. Over the course of the incubation there was a 31% reduction of soil organic matter content. At the same time, in competitive systems Cd K(d) significantly decreased, while Zn K(d) significantly increased, and Ni K(d) remained unaffected. This study shows that sewage sludge-amended soils may change in their ability to sorb heavy metals over time at high metal concentrations. The data suggest that Cd is likely to be of most environmental significance in such soils, since it exhibited decreased sorption under competitive conditions and as the organic matter content of the soil was reduced. The potential for long-term release of metals should be considered in the risk assessment associated with sewage sludge addition to soils, particularly in climates where degradation of organic matter is likely to be enhanced.

Effect of dissolved organic carbon on zinc solubility in incubated biosolids-amended soils.

Soil organic carbon (SOC) and dissolved organic carbon (DOC) affect long-term heavy metal solubility in biosolids-amended soils, but their role needs to be further studied under Mediterranean climatic conditions. We investigated Zn solubility, as assessed by water extraction, in two typical Greek soils amended with biosolids at 0, 20, and 100 Mg ha(-1) during a 310-d incubation period. It was found that SOC decreased by nearly 30% over time in the 100 Mg ha(-1) treatment. There was evidence that DOC affected Zn solubility, because DOC increased significantly on Day 23, probably due to a flush in microbial activity, and water-extractable Zn followed the same trend. After that, both DOC and water-extractable Zn decreased back to values similar to those of the unamended soils. Although Zn solubility did not increase overall even at high biosolids application rates, this study shows that time-limited fluctuations in Zn solubility due to sudden DOC flushes, can be significant, and need to be further investigated.

Boron remobilization at low boron supply in olive (Olea europaea) in relation to leaf and phloem mannitol concentrations.

For plant species in which a considerable portion of the photoassimilates are translocated in the phloem as sugar alcohols, boron is freely translocated from mature organs to growing tissues. However, the effects of decreased plant boron status on boron remobilization are poorly understood. We conducted a growth chamber experiment (CE) and a field experiment (FE) to study the effects of low boron supply on boron remobilization in olive (Olea europaea L.), a species that transports considerable amounts of mannitol in the phloem. For the CE, several physiological parameters were compared between control (B+) and boron-deficient olive plants (B-) during the expansion of new leaves. Boron remobilization was assessed by measuring boron content of selected leaves at the beginning and at the end of the CE. As expected, boron was remobilized from mature leaves to young leaves of B+ plants; however, considerable boron remobilization was also observed in B- plants, suggesting a mechanism whereby olive can sustain a minimum boron supply for growth of new tissues despite an insufficient external boron supply. Boron deficiency caused inhibition of new growth but had no effect on photosynthetic capacity per unit leaf surface area of young and mature leaves, thereby altering the carbon utilization pattern and resulting in carbon allocation to structures within the source leaves and accumulation of soluble carbohydrates. Specifically, in mature B- leaves in the CE and in B- leaves in the FE, mannitol concentration on a leaf water content basis increased by 48 and 27% respectively, compared with controls. Carbon export ability (assessed by both phloem anatomy and phloem exudate composition of FE leaves) was enhanced at low boron supply. We conclude that, at low boron supply, increased mannitol concentrations maintain boron remobilization from source leaves to boron-demanding sink leaves.

A review of the distribution coefficients of trace elements in soils: influence of sorption system, element characteristics, and soil colloidal properties.

Knowledge about the behavior and reactions of separate soil components with trace elements (TEs) and their distribution coefficients (Kds) in soils is a key issue in assessing the mobility and retention of TEs. Thus, the fate of TEs and the toxic risk they pose depend crucially on their Kd in soil. This article reviews the Kd of TEs in soils as affected by the sorption system, element characteristics, and soil colloidal properties. The sorption mechanism, determining factors, favorable conditions, and competitive ions on the sorption and Kd of TEs are also discussed here. This review demonstrates that the Kd value of TEs does not only depend on inorganic and organic soil constituents, but also on the nature and characteristics of the elements involved as well as on their competition for sorption sites. The Kd value of TEs is mainly affected by individual or competitive sorption systems. Generally, the sorption in competitive systems is lower than in mono-metal sorption systems. More strongly sorbed elements, such as Pb and Cu, are less affected by competition than mobile elements, such as Cd, Ni, and Zn. The sorption preference exhibited by soils for elements over others may be due to: (i) the hydrolysis constant, (ii) the atomic weight, (iii) the ionic radius, and subsequently the hydrated radius, and (iv) its Misono softness value. Moreover, element concentrations in the test solution mainly affect the Kd values. Mostly, values of Kd decrease as the concentration of the included cation increases in the test solution. Additionally, the Kd of TEs is controlled by the sorption characteristics of soils, such as pH, clay minerals, soil organic matter, Fe and Mn oxides, and calcium carbonate. However, more research is required to verify the practical utilization of studying Kd of TEs in soils as a reliable indicator for assessing the remediation process of toxic metals in soils and waters.