Inferring chemical effects on carbon flows in aquatic food webs: Methodology and case study

The majority of ecotoxicological enclosure experiments monitor species abundances at different chemical concentrations. Here, we present a new modelling approach that estimates changes in food web flows from such data and show that population- and food web level effects are revealed that are not apparent from abundance data alone. For the case of cypermethrin in freshwater enclosures, photosynthesis and excretion (d⁻¹) of phytoplankton at 3.643 μg L⁻¹ cypermethrin were 30% lower and 100% higher than in the control, respectively. The ingestion rate of mesozooplankton (d⁻¹) was 6 times higher in the treated enclosures than in the control as food concentration increased with insecticide exposure. With increasing cypermethrin concentrations, nanoflagellates progressively relied on phytoplankton as their main food source, which rendered the food web less stable. We conclude that this tool has excellent potential to analyse the wealth of enclosure data as it only needs species abundance and general constraints.     

The relation between Acid Volatile Sulfides (AVS) and metal accumulation in aquatic invertebrates: Implications of feeding behavior and ecology

The present study evaluates the relationship between Acid Volatile Sulfides (AVS) and metal accumulation in invertebrates with different feeding behavior and ecological preferences. Natural sediments, pore water and surface water, together with benthic and epibenthic invertebrates were sampled at 28 Flemish lowland rivers. Different metals as well as metal binding sediment characteristics including AVS were measured and multiple regression was used to study their relationship with accumulated metals in the invertebrates taxa.Bioaccumulation in the benthic taxa was primarily influenced by total metal concentrations in the sediment. Regarding the epibenthic taxa metal accumulation was mostly explained by the more bioavailable metal fractions in both the sediment and the water. AVS concentrations were generally better correlated with metal accumulation in the epibenthic invertebrates, rather than with the benthic taxa. Our results indicated that the relation between AVS and metal accumulation in aquatic invertebrates is highly dependent on feeding behavior and ecology.     

Comparison of summer and winter California central valley aerosol distributions from lidar and MODIS measurements

Aerosol distributions from two aircraft lidar campaigns conducted in the California Central Valley are compared in order to identify seasonal variations. Aircraft lidar flights were conducted in June 2003 and February 2007. While the ground PM_2.5 (particulate matter with diameter ≤ 2.5 μm) concentration was highest in the winter, the aerosol optical depth (AOD) measured from the MODIS and lidar instruments was highest in the summer. A multiyear seasonal comparison shows that PM_2.5 in the winter can exceed summer PM_2.5 by 68%, while summer AOD from MODIS exceeds winter AOD by 29%. Warmer temperatures and wildfires in the summer produce elevated aerosol layers that are detected by satellite measurements, but not necessarily by surface particulate matter monitors. Temperature inversions, especially during the winter, contribute to higher PM_2.5 measurements at the surface. Measurements of the mixing layer height from lidar instruments provide valuable information needed to understand the correlation between satellite measurements of AOD and in situ measurements of PM_2.5. Lidar measurements also reflect the ammonium nitrate chemistry observed in the San Joaquin Valley, which may explain the discrepancy between the MODIS AOD and PM_2.5 measurements.     

A multi-approach monitoring of particulate matter, metals and PAHs in an urban street canyon

For the first time until now, the results from a prediction model (Atmospheric Dispersion Modelling System (ADMS)-Road) of pollutant dispersion in a street canyon were compared to the results obtained from biomonitors. In particular, the instrumental monitoring of particulate matter (PM10) and the biomonitoring of 14 polycyclic aromatic hydrocarbons (PAHs) and 11 metals by Quercus ilex leaves and Hypnum cupressiforme moss bags, acting as long- and short-term accumulators, respectively, were carried out. For both PAHs and metals, similar bioaccumulation trends were observed, with higher concentrations in biomonitors exposed at the leeward canyon side, affected by primary air vortex. The major pollutant accumulation at the leeward side was also predicted by the ADMS-Road model, on the basis of the prevailing wind direction that determines different exposure of the street canyon sides to pollutants emitted by vehicular traffic. A clear vertical (3, 6 and 9 m) distribution gradient of pollutants was not observed, so that both the model and biomonitoring results suggested that local air turbulences in the street canyon could contribute to uniform pollutant distribution at different heights.     

Reproduction and biochemical responses in Enchytraeus albidus (Oligochaeta) to zinc or cadmium exposures

To better understand chemical modes of action, emphasis has been given to stress responses at lower levels of biological organization. Cholinesterases and antioxidant defenses are among the most used biomarkers due to their crucial role in the neurocholinergic transmission and in cell homeostasis preventing DNA damage, enzymatic inactivation and lipid peroxidation. The main goal of this study was to investigate the effects of zinc and cadmium on survival and reproduction of E. albidus and to assess metals oxidative stress potential and neurotoxic effects at concentrations that affected reproduction. Both metals affected the enchytraeids’ survival and reproduction and induced significant changes in the antioxidant defenses as well as increased lipid peroxidation, indicating oxidative damage. This study demonstrates that determining effects at different levels of biological organization can give better information on the physiological responses of enchytraeids in metal contamination events and further unravel the mechanistic processes dealing with metal stress.     

Petroleum refinery stripped sour water treatment using the activated sludge process

A pilot study was performed over 91 days to determine if the activated sludge process could treat a segregated stripped sour water (SSW) stream from a petroleum refinery. The study was performed in two periods. The first period was terminated after 19 days, as a result of excessive sludge bulking. The elimination of sludge bulking during the 70-day second period is attributed to operational changes, which included aerating the influent to oxidize reduced sulfur, adjusting the influent pH, and adding micronutrients to satisfy biological requirements. The pilot plant provided a chemical oxygen demand (COD) removal of up to 93%. Nitrification was achieved, with effluent ammonia values < 1 mg-N/L. These results indicate that direct treatment of SSW with the activated sludge process is possible and has direct application to full-scale petroleum refinery wastewater plant upgrades.     

Functional redundancy and food web functioning in linuron-exposed ecosystems

An extensive data set describing effects of the herbicide linuron on macrophyte-dominated microcosms was analysed with a food web model to assess effects on ecosystem functioning. We showed that sensitive phytoplankton and periphyton groups in the diets of heterotrophs were gradually replaced by more tolerant phytoplankton species as linuron concentrations increased. This diet shift--showing redundancy among phytoplankton species--allowed heterotrophs to maintain their functions in the contaminated microcosms. On an ecosystem level, total gross primary production was up to hundred times lower in the treated microcosms but the uptake of dissolved organic carbon by bacteria and mixotrophs was less sensitive. Food web efficiency was not consistently lower in the treated microcosms. We conclude that linuron predominantly affected the macrophytes but did not alter the overall functioning of the surrounding planktonic food web. Therefore, a risk assessment that protects macrophyte growth also protects the functioning of macrophyte-dominated microcosms.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): a three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth-gastric-intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET - 63.1; HCl - 51.8; PBET - 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils - characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents - the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.