The water-soluble fraction of potentially toxic elements in contaminated soils: relationships between ecotoxicity, solubility and geochemical reactivity

To better understand the impacts posed by soil contamination to aquatic ecosystems it is crucial to characterise the links between ecotoxicity, chemical availability and geochemical reactivity of potentially toxic elements (PTE’s) in soils. We evaluated the adverse effects of water extracts obtained from soils contaminated by chemical industry and mining, using a test battery including organisms from different trophic levels (bacteria, algae and daphnids). These tests provided a quick assessment of the ecotoxicity of soils with respect to possible adverse effects on aquatic organisms although the ecotoxicological responses could be related to the solubility of PTE’s only to a limited extent.The analysis of results of bioassays together with the chemical characterisation of water extracts provided additional relevant insight into the role of conductivity, pH, Al, Fe, and Mn of soil extracts on toxicity to organisms. Furthermore, an important conclusion of this study was that the toxicity of extracts to the aquatic organisms could also be related to the soil properties (pH, Org C and Fe_ox) and to the reactivity of PTE’s in soils which in fact control the soluble fraction of the contaminants.The combined assessment of ecotoxicity in water fractions, solubility and geochemical reactivity of PTE’s in soils provided a more comprehensive understanding of the bioavailability of inorganic contaminants than ecotoxicological or chemical studies alone and can therefore be most useful for environmental risks assessment of contaminated soils.     

Salt marsh macrophyte Phragmites australis strategies assessment for its dominance in mercury-contaminated coastal lagoon (Ria de Aveiro, Portugal)

Introduction and aims

The dominance of a plant species in highly metal-contaminated areas reflects its tolerance or adaptability potential to these scenarios. Hence, plants with high adaptability and/or tolerance to exceptionally high metal-contaminated scenarios may help protect environmental degradation. The present study aimed to assess the strategies adopted by common reed, Phragmites australis for its dominance in highly mercury-contaminated Ria de Aveiro coastal lagoon (Portugal).

Materials and methods

Both plant samples and the sediments vegetated by monospecific stand of Phragmites australis were collected in five replicates from mercury-free (reference) and contaminated sites during low tide between March 2006 and January 2007. The sediments?? physico-chemical traits, plant dry mass, uptake, partitioning, and transfer of mercury were evaluated during growing season (spring, summer, autumn, and winter) of P. australis. Redox potential and pH of the sediment around roots were measured in situ using a WTW-pH 330i meter. Dried sediments were incinerated for 4?h at 500??C for the estimation of organic matter whereas plant samples were oven-dried at 60??C till constant weight for plant dry mass determination. Mercury concentrations in sediments and plant parts were determined by atomic absorption spectrometry with thermal decomposition, using an advanced mercury analyzer (LECO 254) and maintaining the accuracy and precision of the analytical methodologies. In addition, mercury bioaccumulation and translocation factors were also determined to differentiate the accumulation of mercury and its subsequent translocation to plant parts in P. australis.

Results and conclusions

P. australis root exhibited the highest mercury accumulation followed by rhizome and leaves during the reproductive phase (autumn). During the same phase, P. australis exhibited ??5 times less mercury-translocation factor (0.03 in leaf) when compared with the highest mercury bioaccumulation factor for root (0.14). Moreover, seasonal variations differentially impacted the studied parameters. P. australis?? extraordinary ability to (a) pool the maximum mercury in its roots and rhizomes, (b) protect its leaf against mercury toxicity by adopting the mercury exclusion, and (c) adjust the rhizosphere-sediment environment during the seasonal changes significantly helps to withstand the highly mercury-contaminated Ria de Aveiro lagoon. The current study implies that P. australis has enough potential to be used for mercury stabilization and restoration of sediments/soils rich in mercury as well.     

A review of regulatory decisions for environmental protection: part I - challenges in the implementation of national soil policies

Since many soil studies have already revealed the possible risks to human health and the environment arising from contaminated soils it is therefore crucial to preserve soil quality under current and future conditions. In the last three decades a number of countries already introduced national policies and practices for the management of contaminated sites, and in 2002, an EU Thematic Strategy for Soil Protection was proposed by the European Commission. In this paper we review and analyse several national contaminated land policy regimes already in place in order to assess common elements and to identify specific needs in the development of national soil policies. We propose a framework that combines the D-P-S-I-R structure of policy evaluation with the Source-Pathway-Receptor approach to health risk assessment to support the development of effective country specific regulatory decisions for managing contaminated land in countries where these are yet to be implemented. The framework proposed allows decision makers to effectively use available information and to identify existing data gaps. As a result it is apparent that while there are technical aspects of site characterisation, risk assessment and remediation processes that could be commonly implemented at an EU level there are certain trans-scientific aspects that require political choices and need to be customized by EU Member States.     

Long-term trends in mercury and PCB congener concentrations in gannet (Morus bassanus) eggs in Britain

Gannet (Morus bassanus) eggs from Bass Rock (North Sea) and Ailsa Craig (eastern Atlantic) were monitored for PCB congeners (1990-2004) and total mercury (1974-2004). Congener profiles for both colonies were dominated by PCBs 153, 138, 180, 118 and 170. All declined in concentration at Ailsa Craig but some (153, 170, 180) remained stable or increased slightly at Bass Rock. Egg congener concentrations at Bass Rock were typically 10-fold higher than at Ailsa Craig by 2002, and Principal Component Analysis indicated that colony differences were driven by the dominant congeners. Egg mercury concentrations were significantly lower at Bass Rock than at Ailsa Craig and temporal trends differed, there being a significant decline at Ailsa Craig but a marginal increase at Bass Rock. Our results suggest there may be differences in contamination between the eastern Atlantic and North Sea and/or there are colony differences in prey selection and associated contaminant loads.     

Measurement of surface ozone and its precursors in an urban area in South Brazil

Weekly and seasonal variations of surface ozone and their precursors – nitrogen oxides, carbon monoxide-associated with meteorological parameters (wind direction, temperature, solar radiation) – are reported. Measurements were performed continuously during 2006 at two sampling stations located in the metropolitan area of Porto Alegre, Brazil. Results have shown that O₃ concentrations remained almost constant between weekdays. Levels of NO_x precursors decreased especially on Sundays, due to lighter traffic. The seasonal variation has shown a maximum O₃ concentration during summer and spring while NO_x and NO₂ have maxima at the colder months. The daily cycle of highest ozone concentrations reveals a lower nightly level and an inverse relation between O₃ and NO_x, evidencing the photochemical formation of O₃. There are seasonal variation and source heterogeneity.     

Ammonia emissions from naturally ventilated dairy cattle buildings and outdoor concrete yards in Portugal

There is a lack of information on ammonia (NH₃) emissions from cattle housing systems in Mediterranean countries, with most published data deriving from NW Europe. An investigation was carried out in NW Portugal to quantify NH₃ emissions for the main types of dairy cattle buildings in Portugal, i.e. naturally ventilated buildings and outdoor concrete yards, and to derive robust emission factors (EFs) for these conditions and compare with EFs used elsewhere in Europe. Measurements were made throughout a 12-month period using the passive flux sampling method in the livestock buildings and the equilibrium concentration technique in outdoor yards.The mean NH₃ emission factor for the whole housing system (buildings + outdoor yards) was 43.7 g NH₃–N LU^?1 day^?1 and for outdoor concrete yards used by dairy cattle was 26.6 g NH₃–N LU^?1 day^?1. Expressing NH₃ emission in terms of the quantity of liquid milk produced gave similar values across the three dairy farms studied (with a mean of 2.3 kg N ton-milk^?1 produced) and may have advantages when comparing different farming systems. In dairy houses with outdoor yards, NH₃ emissions from the yard area contributed to 69–92% of total emissions from this housing system. Emissions were particularly important during spring and summer seasons from outdoor yards with NH₃ emitted in this period accounting for about 72% of annual emissions from outdoor yards. Mean NH₃ emission factors derived for this freestall housing system and outdoor concrete yards used by dairy cattle in Portugal were higher than those measured in northern Europe. In addition, values of animal N excretion estimated in this study were greater than official National standard values. If these emissions are typical for Portuguese dairy systems, then the current National inventory underestimates emissions from this source in NW of Portugal, because of the use of lower standard values of N excretion by dairy cattle.     

Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells

Purpose

The sorption of sulfamethoxazole, a frequently detected pharmaceutical compound in the environment, onto walnut shells was evaluated.

Methods

The sorption proprieties of the raw sorbent were chemically modified and two additional samples were obtained, respectively HCl and NaOH treated. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric (TG/DTG) techniques were applied to investigate the effect of the chemical treatments on the shell surface morphology and chemistry. Sorption experiments to investigate the pH effect on the process were carried out between pH?2 and 8.

Results

The chemical treatment did not substantially alter the structure of the sorbent (physical and textural characteristics) but modified the surface chemistry of the sorbent (acid?Cbase properties, point of zero charge??pH_pzc). The solution pH influences both the sorbent??s surface charge and sulfamethoxazole speciation. The best removal efficiencies were obtained for lower pH values where the neutral and cationic sulfamethoxazole forms are present in the solution. Langmuir and Freundlich isotherms were applied to the experimental adsorption data for sulfamethoxazole sorption at pH?2, 4, and 7 onto raw walnut shell. No statistical difference was found between the two models except for the pH?2 experimental data to which the Freundlich model fitted better.

Conclusion

Sorption of sulfamethoxazole was found to be highly pH dependent in the entire pH range studied and for both raw and treated sorbent.     

Soil-plant-animal transfer models to improve soil protection guidelines: a case study from Portugal

Food chain models are essential tools to assess risks of soil contamination in view of product quality including fodder crops and animal products. Here we link soil to plant transfer (SPT) models for potentially toxic elements (PTEs) including As, Ba, Cd, Co, Cu, Hg, Ni, Pb, Sb, U and Zn with models describing accumulation in animal organs. Current EU standards for food products and acceptable daily intake levels (ADI) for humans were used as critical limits. The combined model is used to assess the impact of soil contamination on animal health, product quality and human health using data from 100 arable fields. Results indicate that 42 existing arable fields near industrial and mining sites are unsuitable for animal grazing in view of food safety due to elevated intake of Cd, Cu, Hg and Pb by cows and sheep. At 10 sites daily intake levels of As by cows exceeded threshold concentrations regarding the quality of animal products.The food chain model also was used inversely to derive soil threshold concentrations in view of EU fodder standards. Calculated threshold levels in soil for As, Cd, Cu, Pb, Hg and Zn appear to be in line with those proposed or used in other EU countries. As such the approach applied here can form a conceptual basis for a more harmonized risk assessment strategy regarding the protection of animal and human health.     

Nutrients and nonessential elements in soil after 11 years of wastewater irrigation

Irrigation of citrus (Citrus aurantium L. × Citrus paradise Macf.) with urban reclaimed wastewater (RWW) can be economical and conserve fresh water. However, concerns remain regarding its deleterious effects on soil quality. We investigated the ionic speciation (ISP) of RWW and potential impacts of 11 yr of irrigation with RWW on soil quality, compared with well-water (WW) irrigation. Most of nutrients (～53-99%) in RWW are free ionic species and readily available for plant uptake, such as: NH(4+), NO(3-), K(+), Ca(2+), Mg(2+), SO(4)(2-), H(3)BO(3), Cl(-), Fe(2+), Mn(2+), Zn(2+), Co(2+), and Ni(2+), whereas more than about 80% of Cu, Cr, Pb, and Al are complexed with CO(3-), OH(-), and/or organic matter. The RWW irrigation increased the availability and total concentrations of nutrients and nonessential elements, and soil salinity and sodicity by two to three times compared with WW-irrigated soils. Although RWW irrigation changed many soil parameters, no difference in citrus yield was observed. The risk of negative impacts from RWW irrigation on soil quality appears to be minimal because of: (i) adequate quality of RWW, according to USEPA limits; (ii) low concentrations of metals in soil after 11 yr of irrigation with RWW; and (iii) rapid leaching of salts in RWW-irrigated soil during the rainy season.