Assessing and forecasting the impacts of global change on Mediterranean rivers. The SCARCE Consolider project on Iberian basins

Introduction

The Consolider-Ingenio 2010 project SCARCE, with the full title ??Assessing and predicting effects on water quantity and quality in Iberian Rivers caused by global change?? aims to examine and predict the relevance of global change on water availability, water quality, and ecosystem services in Mediterranean river basins of the Iberian Peninsula, as well as their socio-economic impacts. Starting in December 2009, it brought together a multidisciplinary team of 11 partner Spanish institutions, as well as the active involvement of water authorities, river basin managers, and other relevant agents as stakeholders.

Methods

The study areas are the Llobregat, Ebro, Jucar, and Guadalquivir river basins. These basins have been included in previous studies and projects, the majority of whom considered some of the aspects included in SCARCE but individually. Historical data will be used as a starting point of the project but also to obtain longer time series. The main added value of SCARCE project is the inclusion of scientific disciplines ranging from hydrology, geomorphology, ecology, chemistry, and ecotoxicology, to engineering, modeling, and economy, in an unprecedented effort in the Mediterranean area. The project performs data mining, field, and lab research as well as modeling and upscaling of the findings to apply them to the entire river basin.

Results

Scales ranging from the laboratory to river basins are addressed with the potential to help improve river basin management. The project emphasizes, thus, linking basic research and management practices in a single framework. In fact, one of the main objectives of SCARCE is to act as a bridge between the scientific and the management and to transform research results on management keys and tools for improving the River Basin Management Plans. Here, we outline the general structure of the project and the activities conducted within the ten Work Packages of SCARCE.     

Survey of phthalates, alkylphenols, bisphenol A and herbicides in Spanish source waters intended for bottling

Background, aim and scope

Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination.

Materials and methods

Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed.

Results and discussion

Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77?C124?%) and limits of quantification were between 0.0004 and 0.029???g/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018???g/L for octylphenol to 0.970???g/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115???g/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds.

Conclusions

Target compounds were detected in a very low concentration and only in very few samples. This indicates the good quality of source waters intended for bottling and the effectiveness of the protection measures adopted in Spain. None of the samples analysed exceeded the maximum legislated levels for drinking water both in Spain and in the European Union.     

Biomonitoring of pyrethroid exposure among rural and urban populations in northern Poland

The aim of this study was to determine for the first time in Poland, levels of exposure to synthetic pyrethroids in preschool and school age children and their parents living in urban and rural areas. For this purpose concentrations of pyrethroid metabolites: 3-phenoxybenzoic acid (3-PBA), 2,2-dibromovinyl-2,2-dimethylcyclopropanecarboxylic acid (Br₂CA), cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (cis-Cl₂CA) and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (trans-Cl₂CA) were determined in 374 urine samples using a validated GC–MS method.     

Product Guide/1975

Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C₁ and C₂ hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.     

The influence of metal speciation on the bioavailability and sub-cellular distribution of cadmium to the terrestrial isopod, Porcellio dilatatus

Cadmium is a non-essential toxic metal that is able to bioaccumulate in both flora fauna and has the potential to biomagnify in some food chains. However, the form in which cadmium is presented to consumers can alter the bioavailability and possibly the internal distribution of assimilated Cd. Previous studies in our laboratory highlighted differences in Cd assimilation among isopods when they were provided with a plant-based food with either Cd biologically incorporated into plant tissue or superficially amended with ionic Cd(2+). Cd is known for its high affinity for sulphur ligands in cysteine residues which form the basis for metal-binding proteins such as metallothionein. This study compares Cd assimilation efficiency (AE) in Porcellio dilatatus fed with food amended with either cadmium cysteinate or cadmium nitrate in an examination of the influence of Cd speciation on metal bioavailability followed by an examination of the sub-cellular distribution using a centrifugal fractionation protocol. As hypothesized the AE of Cd among isopods fed with Cd(NO(3))(2) (64%, SE=5%) was higher than AE for isopods fed with Cd(Cys)(2) (20%, SE=3%). The sub-cellular distribution also depended on the Cd species provided. Those isopods fed Cd(Cys)(2) allocated significantly more Cd to the cell debris and organelles fractions at the expense of allocation to metal-rich granules (MRG). The significance of the difference in sub-cellular distribution with regard to toxicity is discussed. This paper demonstrates that the assimilation and internal detoxification of Cd is dependent on the chemical form of Cd presented to the isopod.     

Comparision of the waterborne and dietary routes of exposure on the effects of Benzo(a)pyrene on biotransformation pathways in Nile tilapia (Oreochromis niloticus)

BaP is one of the most studied PAH, due to its ubiquitous presence in aquatic environments and toxicity to aquatic organisms. The main goal of this study was to assess BaP effects in Nile Tilapia after waterborne and dietary exposures, through the evaluation of EROD and GST activities in liver, gills and intestine, and BaP metabolites in bile; and also to evaluate the usefulness of these commonly used biomarkers after two different routes of exposure. Waterborne exposure to BaP led to a significant induction of EROD in all tissues analyzed (644%, 1640% and 2880% in relation to solvent in liver, gill and intestine respectively) while in dietary exposures EROD was induced only in intestine (3143%) after exposure to high BaP concentrations. GST activities with CDNB were slightly induced in liver (40%) and in gill (66%) after water exposure to BaP, and in intestine after dietary exposure to low BaP concentrations (182%). BaP metabolites in bile increased after both exposure routes, and were highly correlated with EROD activity after water exposure. In summary, this work has shown that the effects of BaP on biotransformation pathways depend on the route of exposure. Moreover, barrier tissues like gills and intestine also have an important role in the first-pass metabolism of BaP, reducing the amount of parent compound that reaches the liver to be metabolized. For that reason, EROD activity as a biomarker of exposure should also be applied in extrahepatic organs, like gills and intestine, in monitoring studies. Biliary BaP type metabolites are good reflectors of contamination levels under both exposure routes, while GST activity with CDNB as substrate, as a phase II enzyme, does not seem a reliable biomarker of exposure to BaP regardless the route of exposure.     

Non-invasive matrices in human biomonitoring: a review

Humans and other living organisms are exposed to a variety of chemical pollutants that are released into the environment as a consequence of anthropogenic activities. Environmental pollutants are incorporated into the organism by different routes and can then be stored and distributed in different tissues, which leads to an internal concentration that can induce different alterations, adverse effects and/or diseases. Control measures should be taken to avoid these effects and human biomonitoring is a very useful tool that can contribute to this aim. Human biomonitoring uses different matrices to measure the target chemicals depending on the chemical, the amount of matrix necessary for the analysis and the detection limit (LOD) of the analytical technique. Blood is the ideal matrix for most chemicals due to its contact with the whole organism and its equilibrium with organs and tissues where chemicals are stored. However, it has an important disadvantage of being an invasive matrix. The development of new methodology and modern analytical techniques has allowed the use of other matrices that are less or non-invasive, such as saliva, urine, meconium, nails, hair, and semen or breast milk. The presence of a chemical in these matrices reflects an exposure, but correlations between levels in non-invasive matrices and blood must be established to ensure that these levels are related to the total body burden. The development of new biomarkers that are measurable in these matrices will improve non-invasive biomonitoring. This paper reviews studies that measure Cd, Pb, Hg, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides and phthalates in non-invasive matrices, the most used techniques for measurements and what alternative techniques are available.     

Levels of PCDD/F in adipose tissue on non-occupationally exposed subjects living near a hazardous waste incinerator in Catalonia, Spain

The potential adverse effects on human health of hazardous waste incinerators (HWIs) are a subject of concern. The construction of the first and till now only HWI in Spain finished in 1999. In 2007, after approximately 9 years of regular operations in the facility, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined by HRGC/HRMS in samples of adipose tissue of 15 autopsied subjects living in the area under potential impact of the HWI (Constantí, Tarragona County, Catalonia). These data were compared with the levels found in two previous surveys performed in 1998 (baseline) and 2002. The current mean PCDD/F concentration in adipose tissue was 14.6 pg WHO-TEQ/g of fat (range: 3.3–55.4 pg WHO-TEQ/g of fat). It means significant changes (a reduction of 64% and an increase of 47%) in the mean PCDD/F levels in comparison to those found in 1998 and 2002: 40.1 and 9.9 pg WHO-TEQ/g of fat, respectively. Women showed higher levels of PCDD/F than men (23.8 vs 11.2 pg WHO-TEQ/g of fat). The increase in the last 5 years would not be directly attributable to exposure to PCDD/F emitted by the HWI, as other biological monitors such as human plasma and milk decreased during the same period.     

Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.