Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Source identification of sulphate forming salts on sandstones from monuments in Salamanca,Spain—a stable isotope approach

Background, aim and scope  

Salt efflorescences markedly contribute to the alteration and deterioration of building material, in this case the Villamayor Sandstone of the facades in the Old Town of Salamanca, Spain (United Nations Educational, Scientific and Cultural Organization world cultural heritage site). A better understanding of the mechanisms of salt formation and the involved elements would allow more precise measures in monument conservation. The magnesium which is required for the salt precipitation originates from selective processes of hydrolysis. The source of sulphate, however, is presently not as clear. Identifying the source of the sulphur was the main goal of this research. Isotope ratio measurement of δ³⁴S and δ¹⁸O was used to clarify the origins of Mg sulphate salts.     

Mercury, methylmercury, and selenium in blood of bird species from Doñana National Park (Southwestern Spain) after a mining accident

Total mercury (Hg), monomethylmercury (MeHg), and selenium (Se) were determined in blood of 11 bird species living in Doñana National Park (DNP, Southwestern Spain) and the surrounding area in 1999 and 2000 after a mine spill accident. The total Hg contents found varied from 1.00 to 587 ng/mL, with an MeHg percentage higher than 80 %, except in mallard species. In all the cases, the concentrations found were below the threshold of high risk for the bird populations. The parameters which most affected the accumulation of Hg and MeHg in the birds studied were, first, species, or trophic position, and second sampling area. Age does not seem to have a great influence on the content of Hg in the blood of these birds. The levels of Se found ranged from 108 to 873 ng/mL, and they were not affected by species, trophic level, age, or sampling area. The blood Hg concentrations of birds living in the area directly affected by the toxic mud, outside the park, were higher than those found in the other birds, and this could be explained by the mine spill accident happened in 1998.     

Population characteristics of young African women influencing prenatal exposure to DDT (Manhiça, Mozambique)

The concentrations of dichlorodiphenyltrichloroethane (DDT) compounds in cord blood of 214 children born between 2003 and 2006 in Manhiça (Mozambique) have been determined. In this time interval, corresponding to the period before DDT reintroduction for indoor residual spraying, the observed values averaged 0.8 and 0.4 ng/ml for 4,4′-dichlorodiphenyldichloroethylene (4,4′-DDE) and 4,4′-DDT, respectively, and were similar to those found in western countries. However, the 4,4′-DDT/4,4′-DDE ratio was high indicating that the inputs of these compounds arriving to children in utero originated from recent uses of the insecticide. The strongest factor affecting DDT concentration was parity. A well-defined decreasing concentration trend was observed for the cord blood concentrations in the period of study. The trend was also observed for multiparae and primiparae mothers independently. Children from multiparae women showed much lower concentrations than primiparae women. Children from mothers with secondary school level exhibited lower concentrations of these pesticides than mothers with lower degree of education.     

Response of microcrustacean communities from the surface—groundwater interface to water contamination in urban river system of the Jarama basin (central Spain)

In order to evaluate the water quality at the surface/groundwater interface (hyporheic zone), the pattern of microcrustacean assemblages in response to environmental stress caused by urban industrial contamination was studied in the Jarama River basin (central Spain) during high water discharges (March and April 2011). The clustering of biological variables and the concentration of urban contaminants in hyporheic waters showed that pristine hyporheic waters have moderate species diversity (two to seven species) and dominance of k strategist stygobites, whereas excessively contaminated sites are devoid by crustaceans. An intermediate level of disturbance in hyporheic waters is associated with a peak of species taxonomic diversity (four to nine species) and proliferation of r strategist more tolerant species. Typical species found in hyporheic zone, e.g., Paracyclops imminutus (Copepoda, Cyclopoida), Cryptocandona vavrai (Ostracoda) and Herpetocypris chevreuxi (Ostracoda), were good indicators of high concentrations of Cr, Mn, Ni, Cd, Pb and VOCs; whereas the stygobites do not show any significant correlation. The effectiveness of hyporheic crustaceans as efficient bioindicators for assessing the current ecological status of river ecosystems is emphasised.     

Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.     

Determination and evaluation of cadmium, lead and nickel in greenhouse soils of Almería (Spain)

This study determines total levels of three (Cd, Pb and Ni) potentially toxic trace elements in western Almería (Spain) greenhouse surface soil horizons using microwave digestion; it establishes the geochemical baseline concentration, and it investigates possible relationships between soil properties and elemental concentrations. The results show that the soil concentration of these heavy metals is lower than mentioned in the European and Spanish normative, but they are higher than those reported by other authors working on agricultural soils. The obtained geochemical baseline concentrations (mg kg(-1)) were: Cd 0.4-0.8, Pb 2.5-89.9 and Ni 16.1-30.7. Using the upper baseline criterion, 88% of greenhouse soils have relatively higher content of heavy metals because of their Cd, Pb and Ni concentration. Moreover, soil properties are related to heavy metals contents suggesting that among Cd, Pb and Ni have a similar origin and those total metal concentrations are controlled primarily by soil compositions.     

Air pollution exposure—the (in)visible risk factor for respiratory diseases

Environmental Science and Pollution Research - There is increasing interest in understanding the role of air pollution as one of the greatest threats to human health worldwide. Nine of 10...     

Bioavailability of pollutants sets risk of exposure to biota and human population in reservoirs from Iguaçu River (Southern Brazil)

Environmental Science and Pollution Research - The Iguaçu River, located at the Southern part of Brazil, has a great socioeconomic and environmental importance due to its high endemic fish...     

Human and ecotoxicological impacts assessment from the Mexican oil industry in the Coatzacoalcos region,as revealed by the USEtox™ model

Human and ecotoxicological impacts were analyzed in the lower basin of the Coatzacoalcos River (Veracruz, State in Mexico). High pollution levels of contaminants from the oil industry have been reported in natural streams and the Coatzacoalcos River and in their sediments. USEtox? model was employed to evaluate environmental fate, exposure, and effect of nine organic compounds (polycyclic aromatic hydrocarbons and one of which was in the group of polychlorinated biphenyls), a heavy metal (lead), and the effect of the industrial wastewater emitted into the river, on the Coatzacoalcos region. Most of these compounds are highly toxic; they bioaccumulate in human and animal tissue, mainly in the fatty tissues and can damage different organs and systemic targets such as the liver, kidney, hormonal system, nervous system, etc., of both humans and wildlife. The model estimates that 96 % (3,247 kg/day) of organic compounds is transferred from the water into air, whereas only 4 % (151 kg/day) remains in the water. In addition, it predicts that humans are mainly exposed to polychlorinated biphenyls (PCBs) congeners (28 and 153) by eating contaminated fish, due to PCBs accumulating in the fish fat tissue. The number of cases of cancer and noncancer (1 in 862 habitants per additional kilogram) is expected to have an increment due to the higher PCBs exposure of human population. Genetic damages in fishes, earthworms, and toads have been observed and related to higher exposure to organic compounds. The relationship between the field reported data and those one predicted by the USEtox? model have been confirmed empirically by using the nonparametric correlation analysis (Spearman's rho). Based on the USEtox model, the environmental stress in the Coatzacoalcos industrial zone is between 2 and 6 orders of magnitude over geometric mean of acute aquatic EC₅₀s. We think that USEtox model can be used to expand the number of substances that have the current water quality guidelines to improve the water management in Mexico.     

Quality of roof runoff waters from an urban region (Gdańsk,Poland)

The paper presents the results of testing of roof runoff waters from buildings in the city of Gdańsk (Poland), carried out as a part of a broader research project aimed at the determination of pollutant levels in precipitation. The analytes determined included volatile organohalogen compounds, petroleum hydrocarbons, Na+, K+, NH4+, Mg2+, Ca2+, F-, Cl-, NO2-, NO3-, PO4(3-), SO4(2-) ions, as well as organonitrogen, organophosphorus and organochlorine pesticides. In addition, the toxicity and pH of the samples were examined. The samples were collected over a period of six months, during or immediately following precipitation events. More than half of the samples (25) were found to be toxic, with inhibition exceeding 20%. The toxicity was weakly correlated to the levels of organonitrogen and organophosphorus pesticides in runoff waters. It was established that at least in some cases the roofing material affected the levels of the pollutants found in the samples.     

Determination of aliphatic and polycyclic aromatic hydrocarbons in atmospheric particulate samples of a coruña city (Spain)

The hydrocarbon composition of atmospheric particulate matter from A Coruña city (Northwest Spain) has been studied. TSP (total suspended particulate) and PM₁₀ (particulate matter with aerodynamic diameter <10 µm) samples were taken over 7 and 4 months at two stations located in residential and industrial sectors of A Coruña city, respectively. The levels of hydrocarbons found in atmospheric particulate samples of A Coruña city are higher than the ones found in other cities over the world. Ratios between the analysed compounds and their sources were established. Both anthropogenic and biogenic origins were found.     

Integrative assessment of coastal pollution in a Ría coastal system (Galicia, NW Spain): correspondence between sediment chemistry and toxicity

Elutriate embryo-larval bioassays with sea-urchins (Paracentrotus lividus) and ascidians (Ciona intestinalis) were conducted concurrently with trace metal analyses as part of an integrative assessment of sediment pollution at Ría de Pontevedra (Galicia, NW Spain). High metal contents in sediments were found in localised areas from the inner part of the estuary indicating a clear anthropogenic influence. In particular, very high Cu, Zn and Pb levels were found at sites P2 and P3, which were also the most toxic to the embryo-larval bioassays. Sediment quality guidelines were used to help in the ecological interpretation of sediment chemistry data and to identify pollutants of concern. Cu and Zn in P3 were consistently above the effects range median (ERM) values, which seem to be good predictors of toxicity to sea-urchin and ascidian embryos. A toxic unit approach, based on published EC(50) values and metal levels in elutriates, was used to assess the harmful ecological effects associated to sediment chemistry. Toxicity detected in P3 may be explained on the basis of the toxic unit model; however, the high toxicity detected at P2 may be attributable not only to the metals quantified in the analyses but also to unmeasured organic pollutants. Multidimensional scaling applied independently to the toxicology and chemistry data resulted in a good agreement between both types of configurations. Moreover, the Mantel test revealed a significant correlation (r(M)=0.481; p=0.019) between metal concentrations and toxicity data profiles, supporting the correspondence between configurations.     

Tire tread wear particles in ambient air—a previously unknown source of human exposure to the biocide 2-mercaptobenzothiazole

Urban particulate matter (PM), asphalt, and tire samples were investigated for their content of benzothiazole and benzothiazole derivates. The purpose of this study was to examine whether wear particles, i.e., tire tread wear or road surface wear, could contribute to atmospheric concentrations of benzothiazole derivatives. Airborne particulate matter (PM₁₀) sampled at a busy street in Stockholm, Sweden, contained on average 17 pg/m³ benzothiazole and 64 pg/m³ 2-mercaptobenzothiazole, and the total suspended particulate-associated benzothiazole and 2-mercaptobenzothiazole concentrations were 199 and 591 pg/m³, respectively. This indicates that tire tread wear may be a major source of these benzothiazoles to urban air PM in Stockholm. Furthermore, 2-mercaptobenzothiazole was determined in urban air particulates for the first time in this study, and its presence in inhalable PM₁₀ implies that the human exposure to this biocide is underestimated. This calls for a revision of the risk assessments of 2-mercaptobenzothiazole exposure to humans which currently is limited to occupational exposure.     

Illegal landfill in Italy (EU)—a multidisciplinary approach

Illegal dumping of solid waste is a matter of recent concern because of its numerous impacts. The regulatory framework of the European Union and Italy is disclosed. Degradation of air, bodies of water, groundwater, and soil can occur in the illegal landfill and surrounding sites causing e.g. acidification, eutrophication global warming and photochemical smog. Animals and plants are subjected to landfill borne pollutants that can damage them seriously. Landfill pollutants have also harmful effects on human beings raising the risk of illness such as cancer and cardiorespiratory disease. Finally illegal landfilling practices lead to economical, aesthetic impacts, and sociological discomfort that lead to multiple collective actions, blockages, and information campaigns, rising sense of belonging.     

Emission of non-methane volatile organic compounds (VOCs) from boreal peatland microcosms—effects of ozone exposure

Non-methane volatile organic compounds (VOCs) emitted from boreal peatland microcosms were semiquantitatively determined using gas chromatography–mass spectrometry techniques in a growth chamber experiment. Furthermore, effects of vegetation composition and different ozone concentrations on these emissions were estimated by multivariate data analyses. The study concentrated on the less-studied VOCs, and isoprene was not analyzed. The analyses suggest that a sedge Eriophorum vaginatum is associated with emissions of the four most-emitted VOC groups (cyclic, aromatic, carbonyl and aliphatic hydrocarbon compounds) and also with VOCs emitted in smaller amounts (terpenoids and N-containing compounds). A woody dwarf shrub Andromeda polifolia was strongly associated with emissions of aromatic, carbonyl and terpenoid compounds. Results suggest that exposure to an ozone concentration of 150 ppb leads to an increased emission of most VOC groups. Emission of aromatic compounds seems to increase linearly with increasing ozone concentration. These observations indicate that peatlands may be a source of a vast range of volatile compounds to the atmosphere. For more accurate assessment of the impact of elevated tropospheric ozone on the terpenoid and non-terpenoid VOC emissions from peatlands, well-replicated open-air ozone-exposure experiments should be conducted.     

Accumulation of As, Cd and selected trace elements in tubers of Scirpus maritimus L. from Doñana marshes (South Spain)

The collapse of a pyrite-mining, tailing dam on 1998 contaminated an area of 4286 ha along the Agrio and Guadiamar river valleys in southern Spain. Over 2700 ha of the Do?ana marshes, an important wintering area for wetland European birds, were contaminated. This study reports analyses of the tubers of Scirpus maritimus (an important food for greylag geese, Anser anser) collected in 2000 in the "Entremuros" (spill-affected area) and in nearby unaffected Do?ana marshes (control areas). In the spill-affected area mean tuber tissue concentrations of Cd (0.25 mg kg-1) and Zn (61 mg kg-1) were greater than in those tubers from the control area (0.02 mg kg-1 for Cd, and 22 mg kg-1 for Zn); values of Cd and Zn in "Entremuros" (samples collected two years after the mine spill) were much smaller than those reported only a few months after the accident. Trace elements (As, Fe, Mn and Tl, and to a lesser extent Cd and Pb) showed a preferential accumulation in the outer skin of tubers. Surprisingly, concentrations of As and Fe were greater in tubers from some marsh sites not affected by the mine-spill than in tubers from the "Entremuros". We suggest that relic river channels within the Do?ana marshes may be contaminated by trace elements from historic mining activities. An exhaustive study of macrophytes and other plant species in this area is recommended to identify potential risks to wildlife.     

High levels of perfluoroalkyl acids in eggs and embryo livers of great cormorant (Phalacrocorax carbo sinensis) and herring gull (Larus argentatus) from Lake Vänern, Sweden

In the eggs and developing chick livers in the two wild bird species, great cormorant and herring gull, the concentrations of a range of 15 perfluoroalkyl acids (PFAAs) were determined. Eggs of the two species were collected from Lake Vänern, Sweden, and analysed either as undeveloped egg (whole egg or separated into yolk and albumen) or incubated until start of the hatching process when the chick liver was removed and analysed. High levels of PFAAs were found in all matrixes except albumen. The predominant PFAA was perfluorooctane sulfonate (PFOS), which was found in the μg/g wet weight (ww) range in some samples of cormorant whole egg, yolk and liver and herring gull egg yolk and liver. The average concentration in yolk was 1,506 ng/g ww in cormorant and 589 ng/g ww in herring gull. The average liver concentrations of PFOS were 583 ng/g ww in cormorant and 508 ng/g ww in herring gull. At these concentrations, biochemical effects in the developing embryo or effects on embryo survival cannot be ruled out. For perfluoroalkyl carboxylates (PFCAs), the liver/egg and liver/yolk concentration ratios increased with PFCA chain length in cormorant but not in herring gull, indicating that chain length could possibly affect egg-to-liver transfer of PFCAs and that species differences may exist.     

High prevalence of infections and pathological changes in burbot (Lota lota) from a polluted lake (Lake Mjøsa,Norway)

The aim of the present study was to investigate whether exposure to high levels of persistent organic pollutants (POPs) affected a fish population in Lake Mjøsa. Lake Mjøsa is known to be contaminated by polybrominated diphenyl ethers (PBDEs), a subgroup of brominated flame retardants from local industrial activities. Fish from Lake Losna, a less contaminated lake located close to Lake Mjøsa, was used as reference (control).The sampling of burbot (Lota lota) was carried out between 2005 and 2008. Hepatic levels of POPs were analysed in burbot from the two lakes, and the fish were examined for bacterial- and parasite infection and histopathological changes. The levels of polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs), and PBDEs were about 10, 15 and 300 times higher in fish from Lake Mjøsa compared to fish from Lake Losna. Mycobacterium salmoniphilum was present in 7% and 35% of the fish from Lake Losna and Lake Mjøsa respectively. Significantly higher number of external and visceral macroscopic lesions, histopathological diffuse changes and granulomas were seen in fish from Lake Mjøsa compared to Lake Losna. Furthermore the parasite infection was higher and the hepatic lipid content was significantly lower in burbot from Lake Mjøsa. The results of the present study suggest that the high level of contamination in Lake Mjøsa could have a negative impact on the health status of wild fish inhabiting the lake.     

Association between fetal exposure to polycyclic aromatic hydrocarbons and low birth weight: a case–control study in Shenzhen,China

Environmental Science and Pollution Research - The potential hazards of polycyclic aromatic hydrocarbons (PAHs) on fetus development have raised widespread concerns in recent years, although...