Levels of chemical and microbiological pollutants in the vicinity of a waste incineration plant and human health risks: temporal trends

In 2007, a program was initiated to monitor air levels of volatile organic compounds (VOCs) and bioaerosols in the vicinity of a municipal solid waste incinerator (MSWI) (Tarragona, Catalonia, Spain). To investigate the temporal trends of chemical and microbiological pollutants, four 6-monthly campaigns were performed. Air samples were collected at different distances and directions from the facility, as well as in reference sites. In general terms, the concentrations of microbiological agents were very similar to those found in urban zones worldwide. The seasonal evaluation of the results showed higher levels of gram-negative bacteria in winter, contrasting with the increase of the airborne amount of total bacteria in summer. On the other hand, the concentrations of VOCs (mean range: 7.6-18.2 μgm⁻³) were typical of suburban zones. The current exposure to those compounds should not mean additional health risks for the population living nearby.     

Occurrence of multiclass UV filters in treated sewage sludge from wastewater treatment plants

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. So far, there is only one extensive survey on the occurrence of UV filter residues in sewage sludge. However, more data are required to draw a reliable picture of the fate and effects of these compounds in the environment. This study attempts to fill this gap through the determination of selected UV filters and derivatives namely 4-methylbenzylidenecamphor, benzophenone-3, octocrylene, ethylhexylmethoxycinnamate, ethylhexyldimethyl PABA, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 4,4′-dihydroxybenzophenone in treated sewage sludge.The target compounds were extracted using pressurized liquid extraction and after this, determined by ultra high resolution liquid chromatography-tandem mass spectrometry. The determination was fast and sensitive, affording limits of detection lower than 19 ng g⁻¹ dry weight (dw) except for 2,4-dihydroxybenzophenone (60 ng g⁻¹ dw). Good recovery rates, especially given the high complexity of sludge matrix (between 70% and 102% except for 2,4-dihydroxybenzophenone (30%)) were achieved.The application of developed method allowed reporting for the first time the occurrence of two major degradation products of benzophenone-3 that have estrogenic activity in sewage sludge: 4,4′-dihydroxybenzophenone (in 5/15 WWTPs) and 4-hydroxybenzophenone (in 1/15 WWTPs). Results revealed the presence of UV filters in 15 wastewater treatment plants in Catalonia (Spain) at concentrations ranging from 0.04 to 9.17 μg g⁻¹ dw.     

Persistence of two neonicotinoid insecticides in wastewater, and in aqueous solutions of surfactants and dissolved organic matter

Wastewater treatment plants receive organic contaminants, such as pesticides, which reach the sewage system from domestic, industrial or agricultural activities. In wastewater, which is a complex mixture of organic and inorganic compounds, biotic or abiotic degradation of contaminants can be affected by the presence of co-solutes. The photodecomposition in natural sunlight of two neonicotinoid insecticides, thiamethoxam and thiacloprid, was investigated in wastewater, aqueous extracts of sewage sludge and in aqueous surfactant solutions, which are abundant in wastewater. Dissipation in the dark was also studied in wastewater, due to reduction of transmitted sunlight in wastewater ponds. With regard to photolysis, thiamethoxam degraded rapidly in all the aqueous solutions. Among them sewage sludge extracts slightly modified (average half-life 17.6 h), wastewater increased (13.7 h) and non-ionic surfactants led, as a family, to the highest dissipation rates (average 6.2 h), with respect to control water (18.7 h). Additionally this pesticide also underwent a slower biodegradation process in wastewater in the dark under anaerobic conditions (around 25 d). A metabolite of thiamethoxam from the biological decomposition in wastewater was identified by HPLC/MS. On the other hand thiacloprid was found to be resistant to photo- and biodecomposition and remained almost unchanged during the experimental periods in all the tested media.     

Oxidative stress, cytoxicity, and cell mortality induced by nano-sized lead in aqueous suspensions

This paper reports on the effect of aqueous and nano-particulated Pb on oxidative stress (lipid peroxidation), cytoxicity, and cell mortality. As determined by the Thiobarbituric Acid Reactive Substances (TBARS) method, only 6 h after incubation aqueous suspensions bearing nano-sized PbO₂, soluble Pb(II), and brain-homogenate only suspensions, were determined to contain as much as ca. 7, 5, and 1 nmol TBARS mg protein⁻¹, respectively. Exposure of human cells (central nervous system, prostate, leukemia, colon, breast, lung cells) to nano-PbO₂ led to cell-growth inhibition values (%) ca. ≤18.7%. Finally, as estimated by the Artemia salina test, cell mortality values were found to show high-survival larvae rates. Microscopic observations revealed that Pb particles were swallowed, but caused no mortality, however.     

Mercury, lead and cadmium in human milk in relation to diet, lifestyle habits and sociodemographic variables in Madrid (Spain)

Background

Although breastfeeding is the ideal way of nurturing infants, it can be a source of exposure to toxicants. This study reports the concentration of Hg, Pb and Cd in breast milk from a sample of women drawn from the general population of the Madrid Region, and explores the association between metal levels and socio-demographic factors, lifestyle habits, diet and environmental exposures, including tobacco smoke, exposure at home and occupational exposures.

Methods

Breast milk was obtained from 100 women (20 mL) at around the third week postpartum. Pb, Cd and Hg levels were determined using Atomic Absorption Spectrometry. Metal levels were log-transformed due to non-normal distribution. Their association with the variables collected by questionnaire was assessed using linear regression models. Separate models were fitted for Hg, Pb and Cd, using univariate linear regression in a first step. Secondly, multivariate linear regression models were adjusted introducing potential confounders specific for each metal. Finally, a test for trend was performed in order to evaluate possible dose-response relationships between metal levels and changes in variables categories.

Results

Geometric mean Hg, Pb and Cd content in milk were 0.53 μg L⁻¹, 15.56 μg L⁻¹, and 1.31 μg L⁻¹, respectively. Decreases in Hg levels in older women and in those with a previous history of pregnancies and lactations suggested clearance of this metal over lifetime, though differences were not statistically significant, probably due to limited sample size. Lead concentrations increased with greater exposure to motor vehicle traffic and higher potato consumption. Increased Cd levels were associated with type of lactation and tended to increase with tobacco smoking.

Conclusions

Surveillance for the presence of heavy metals in human milk is needed. Smoking and dietary habits are the main factors linked to heavy metal levels in breast milk. Our results reinforce the need to strengthen national food safety programs and to further promote avoidance of unhealthy behaviors such as smoking during pregnancy.     

Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

Recent Changes in the Riparian Forest of a Large Regulated Mediterranean River: Implications for Management

The structure of the floodplain forests of the Middle Ebro River (NE Spain) was examined at patch and landscape scales along a three-step chronosequence defined according to the extent of flow regulation-induced hydrogeomorphic changes, with the ultimate purpose of producing baseline information to guide through management and restoration plans. At patch scale, a total of 6,891 stems within 39 plots were registered for species, diameter and health status. The stem density, size class distribution, canopy dieback and mortality were further compared by means of non-parametric tests. At landscape scale, the temporal evolution of the area occupied by forest stands of different ages in the floodplain along the chronosequence was evaluated using four sets of aerial photographs dated in 1927, 1957, 1981 and 2003. The within-patch structure of pioneer forests (<25–30 years old) was characterized by dense and healthy populations of pioneer species (Populus nigra, Salix alba and Tamarix spp.), but the area occupied by these forest types has progressively decreased (up to 37%) since the intensification of river regulation (ca. 1957). In contrast, non-pioneer forests (>25–30 years old) were characterized by declining and sparse P. nigra–S. alba–Tamarix spp. stands, where late-seral species such as Ulmus minor and Fraxinus angustifolia were frequent, but only as small-size stems. At landscape scale, these type of senescent forests have doubled their surface after river regulation was intensified. Populus alba only appeared in the oldest plots recorded (colonized before 1957), suggesting sexual regeneration failure during the last five decades, but usually as healthy and dense stands. Based on these findings, measures principally aimed at recovering some hydrogeomorphic dynamism are recommended to guarantee the self-sustainability of the floodplain forest ecosystem.     

Effect of Hydrothermal Polylactic Acid Degradation on Polymer Molecular Weight and Surface Properties

In the present work, polylactic acid, PLA, samples were degraded by hydrothermal treatment, and then their molecular weights, crystallinity, surface charges and compositions, were determined, respectively, by using viscometry, ¹H NMR, Differential Scanning Calorimetry (DSC), microelectrophoresis and Infra Red spectroscopy methods. The viscometry and ¹H NMR data indicate that the molecular weight, of the polymer, decreases after the hydrothermal treatment. However, the crystalline fractions of the PLA samples, as obtained from the DSC and X-ray data, were not altered after the hydrothermal treatment. Furthermore, the zeta potential data, as determined by microelectrophoresis, show for both non-degraded and degraded PLA, an increase of the polymer surface charge density with the pH of the aqueous phase. However, at acidic pH values, the surface charge density for the degraded PLA was higher as compared to the non degraded one. These differences in surface charge densities of the PLA samples were confirmed by Infrared study, according to which the spectra of degraded polymer show the appearance of carboxyl groups occurring at 1,600 cm⁻¹ at the polymer surface.     

Lichens as an integrating tool for monitoring PAH atmospheric deposition: A comparison with soil, air and pine needles

The aim of this study was to validate lichens as biomonitors of PAH atmospheric deposition; for that, an inter-comparison between the PAH profile and concentrations intercepted in lichens with those of air, soil and pine needles was performed. The study was conducted in a petro-industrial area and the results showed that PAH profiles in lichens were similar to those of the air and pine needles, but completely different from those of soils. Lichens accumulated higher PAH concentrations when compared to the other environmental compartments and its concentrations were significantly and linearly correlated with concentrations of PAHs in soil; we showed that a translation of the lichen PAHs concentrations into regulatory standards is possible, fulfilling one of the most important requirements of using lichens as biomonitors. With lichens we were then able to characterize the air PAHs profile of urban, petro-industrial and background areas.     

Effect of liquid cow manure on andisol properties and atrazine adsorption

Application of animal manure amendments to agricultural soils is a common practice to improve soil fertility through the addition of essential plant nutrients. This practice may increase the potential for atrazine (2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-triazine) leaching due to competition for adsorption sites between the pesticide and dissolved organic carbon (DOC) added through manure. We evaluated the influence of liquid cow manure (LCM) application on soil properties, atrazine adsorption, and the physicochemical controlling mechanisms in an Andisol. The LCM was applied at rates equivalent to 0, 100,000, 200,000, and 300,000 L ha(-1), resulting in treatments S-0, S-100, S-200, and S-300, respectively. The LCM application increased DOC and pH of the soils immediately on addition, but pH returned to S-0 values 30 d after application. The LCM application did not modify atrazine adsorption with the two lowest application rates (S-100 and S-200), but atrazine adsorption was decreased in S-300 (K(f) = 0.96) compared with the control (S-0) (K(f) = 1.19), possibly due to the competitive adsorption of DOC with the pesticide. The Fourier-transformed infrared analysis showed that LCM increased aliphaticity and presence of N-containing groups and polysaccharide-like groups in amended soils; however, these properties did not modify the atrazine interaction in the studied amended soils. Interestingly the addition of DOC to soil at the high application rate (S-300) reduced atrazine adsorption in this rich OM Andisol despite the LCM not raising the concentration of stable organic matter. The application of high rates of liquid manure containing DOC incurs an increased risk of pesticide leaching.