Polycyclic aromatic hydrocarbon sampling in wastewaters using semipermeable membrane devices: accuracy of time-weighted average concentration estimations of truly dissolved compounds

Semipermeable membrane devices (SPMDs) previously spiked with performance reference compounds were exposed in wastewater. After 6 days of exposure, 13 polycyclic aromatic hydrocarbons (PAHs) were quantified in SPMDs. Exchange rate constants and time-weighted average (TWA) concentrations of SPMD-available PAHs in water were calculated. The bias of using SPMDs to estimate an actual TWA concentration if the concentration in water fluctuates, as can be expected in wastewater, was studied with numerical simulations. The bias increased with the exchange rate constant. However, most exchange rate constants evaluated in SPMDs exposed in wastewater were small enough for SPMDs to estimate a TWA concentration of PAHs even when the water concentration varied. TWA-SPMD-available concentrations were always below total dissolved (operationally defined as 0.7 microm) concentrations, indicating that part of the dissolved PAHs was not available for sampling. In situ partitioning coefficients K(DOC) were computed and found to be slightly higher than data from the literature. This confirms that only truly dissolved PAHs should be sampled by SPMDs in wastewater.     

Photodegradation of the steroid hormones 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in dilute aqueous solution

The photochemical transformation of natural estrogenic steroid 17beta-estradiol (E2) and the synthetic oral contraceptive 17alpha-ethinylestradiol (EE2) has been studied in dilute non buffered aqueous solution (pH 5.5-6.0) upon monochromatic (254 nm) and polychromatic (lambda>290 nm) irradiation. Upon irradiation at 254 nm, the quantum yields of E2 and EE2 photolysis were similar and evaluated to be 0.067+/-0.007 and 0.062+/-0.007, respectively. Upon polychromatic excitation, and by using phenol as chemical actinometer, the photolysis efficiencies have been determined to be 0.07+/-0.01 and 0.08+/-0.01 for E2 and EE2, respectively. For both estrogens, photodegradation by-products were identified with GC/MS and LC/MS. In a first step, a model compound--5,6,7,8-tetrahydro-2-naphthol (THN)--, which represents the photoactive phenolic group, was used to obtain basic photoproduct structural informations. Numerous primary and secondary products were observed, corresponding to hydroxylated phenolic- or quinone-type compounds.     

Influence of Technological Process on Biodegradation of PVA/Waxy Starch Blends in an Aerobic and Anaerobic Environment

Improving biodegradability of PVA/starch blends is a reality already documented by a number of works. Admittedly, mechanical properties of products (for example, tensile strength) are somewhat worse, but suitable composition optimizing or chemical modifying of starch may eliminate the problem to a large degree. This work is an attempt to find another potential effect influencing biodegradability, that of technological procedure for producing films from these blends on an extruder. The procedure with a so-called pre-extrusion step (two-stage) and dry-blend (single-stage) produced blends of slightest differences in achieved biodegradability (virtually within limits of experimental error) in aerobic (76 vs. 79%) as well as anaerobic breakdown (48 vs. 52%). Conversely, morphological analysis exhibited superior homogeneity of films prepared by the two-stage process; their tensile strength was also higher.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

Life cycle responses of the midge Chironomus riparius to polycyclic aromatic compound exposure

During acute exposure, polycyclic aromatic compounds (PACs) act mainly by narcosis, but during chronic exposure the same compounds may exert sublethal life cycle effects. The aim of this study was therefore to evaluate the chronic effects of sediment spiked PACs on the emergence of the midge Chironomus riparius. Three isomer pairs were selected, and 28-day LC50 values and 50% emergence times (EMt50) were determined. Concentration-response relationships were observed for phenanthrene, acridine, phenanthridine and acridone. Anthracene and phenanthridone had no effect on total emergence, but did cause a delay in emergence. Calculated porewater LC50 values correlated well with logKow values, suggesting narcosis as mode of action. In contrast, effect concentrations for delay in emergence (EMt50) deviated from narcosis, suggesting a specific mode of action during chronic exposure. It is concluded that emergence is a powerful endpoint to detect life cycle effects of PACs on a key sediment inhabiting invertebrate.     

Substance Flow Analyses of Organic Pollutants in Stockholm

This paper summarizes substance flow analyses for four organic substances in the City of Stockholm, Sweden: diethylhexyl phthalate (DEHP), alkylphenolethoxylates (APEO), polybrominated diphenylethers (PBDE) and chlorinated paraffins (CP). The results indicate that the stocks of APEO, PBDE and CP all are approximately 200–250 tonnes, whereas the DEHP stock is two orders of magnitude larger. Emissions can be linked to imported consumer goods such as electronics (PBDE) and textiles (APEO), and to construction materials (DEHP, CP). For several of the substances considerable amounts remain in the technosphere for a long time, even after use of the substance in new products has been eliminated. For example, the use of DEHP as plasticizer for PVC plastics in cables and floorings has more or less been phased-out, but still these applications make up a stock of some 20,000 tonnes (85% of the total DEHP stock in Stockholm) and emit 28 tonnes of DEHP annually (93% of overall emissions). Likewise, the use of chlorinated paraffins in sealants has been radically reduced, but there are 170 tonnes of CP in sealants in Stockholm making up 75% of the stock, and causing half of the emissions to water and air. These emissions are likely to continue for decades, and the stocks therefore have to be considered when analysing and managing the impact of urban substance flows on the environment.     

Antibacterial behavior of silver-modified clinoptilolite-heulandite rich tuff on coliform microorganisms from wastewater in a column system

The water disinfecting behavior of silver-modified clinoptilolite–heulandite rich tuff (ZSAg) as an antibacterial agent against coliform microorganisms from water in a continuous mode was investigated. Silver recovery from the disinfected effluents by the sodium-modified clinoptilolite–heulandite rich tuff (ZSNa) was also considered. Escherichia coli (ATCC 8739) and total coliform microorganisms, as indicators of microbiological contamination of water, were chosen to achieve the disinfection of synthetic wastewater or municipal wastewater. Ammonium (NH₄⁺) and chloride (Cl⁻) ions were added to the synthetic wastewater as an interfering chemical species on the disinfection processes. The antibacterial activity of the ZSAg as a bactericide was measured by the coliform concentration as evaluated by the APHA method. The amount of silver in the disinfected effluents was determined using atomic absorption spectroscopy. The inactivation of the ZSAg was calculated from the breakthrough curves based on the model reported by Gupta et al. It was found that when the silver concentration in the effluent is less than 0.6 μg/mL, the bacterial survival percentage increased and the volume of disinfected water diminished. The total silver amounts found in the effluent at the end of the disinfection processes varied depending on the water treated (synthetic or municipal wastewater). The presence of NH₄⁺ ions in synthetic wastewater influent notably improved the disinfected water volume (zero NVC/100 mL), in comparison to the disinfection of the same influent without NH₄⁺ ions. A contrary water disinfection behavior was observed in the presence of Cl⁻ ions. The silver recovery does not depend on the mass of the sodium zeolitic bed according with the wastewater to be treated (synthetic or municipal wastewater) and the presence of NH₄⁺ or Cl⁻ ions in the influent also influenced the silver recovery from wastewater. The ZSNa did not have antibacterial activity. Therefore the amount of bactericide agent (silver-modified natural zeolite), coliform microorganisms from water (E. coli or consort of coliform microorganisms) as well as the water quality (synthetic wastewater or municipal wastewater) influenced both the disinfection process and the silver recovery in a column system.     

Chemosensory discrimination of familiar and unfamiliar conspecifics by lizards: implications of field spatial relationships between males

The ability of territorial lizards to discriminate between scents of neighbors and non-neighbors might contribute to decreasing the costs of aggressive interactions. To test this hypothesis, we conducted a field study to analyze the spatial relationships between male Iberian rock-lizards, Lacerta monticola. We then used the same individuals in a laboratory experiment to test whether male lizards can use chemical cues to discriminate between familiar conspecific males (those whose home ranges overlapped) and unfamiliar conspecific males (those whose home ranges did not overlap, and whose home range centers were at least 50 m apart). Differences in tongue-flick rates in the presence of chemical cues suggested that male L. monticola discriminated between odors of familiar and unfamiliar males. The behavioral responses were also dependent on relative differences in body size between the responding male and the unfamiliar male that donated the scent: There was a significant negative correlation between tongue-flick rates emitted in cages of unfamiliar males and the body size differences between males. In contrast, when the donor of the scent was a familiar male, the tongue-flick rate was not dependent on body size differences. These results are compatible with individual discrimination through chemical cues in male L. monticola.     

Particulate matter levels in a South American megacity: the metropolitan area of Lima-Callao,Peru

The temporal and spatial trends in the variability of PM₁₀ and PM_2.5 from 2010 to 2015 in the metropolitan area of Lima-Callao, Peru, are studied and interpreted in this work. The mean annual concentrations of PM₁₀ and PM_2.5 have ranges (averages) of 133–45 μg m^?3 (84 μg m^?3) and 35–16 μg m^?3 (26 μg m^?3) for the monitoring sites under study. In general, the highest annual concentrations are observed in the eastern part of the city, which is a result of the pattern of persistent local winds entering from the coast in a south-southwest direction. Seasonal fluctuations in the particulate matter (PM) concentrations are observed; these can be explained by subsidence thermal inversion. There is also a daytime pattern that corresponds to the peak traffic of a total of 9 million trips a day. The PM_2.5 value is approximately 40% of the PM₁₀ value. This proportion can be explained by PM₁₀ re-suspension due to weather conditions. The long-term trends based on the Theil-Sen estimator reveal decreasing PM₁₀ concentrations on the order of ?4.3 and ?5.3% year^?1 at two stations. For the other stations, no significant trend is observed. The metropolitan area of Lima-Callao is ranked 12th and 16th in terms of PM₁₀ and PM_2.5, respectively, out of 39 megacities. The annual World Health Organization thresholds and national air quality standards are exceeded. A large fraction of the Lima population is exposed to PM concentrations that exceed protection thresholds. Hence, the development of pollution control and reduction measures is paramount.     

A Novel Formulation for Designing a Monitoring Strategy: Application to the Design of a River Quality Monitoring System

In this work, we propose a technique to automatically optimize the monitoring of any distributed indicator (concentration of a substance along a river, blood pressure of a patient over time, etc.) for which a reliable estimate is previously available. From a mathematical point of view, the problem is based on obtaining a reliable estimate of the chosen indicator (e.g., by numerical simulation), and then solving a multi-objective optimization problem (with mixed real and integer variables) whose solution must provide an efficient and satisfactory monitoring strategy. As an illustrative case, we show the steps to follow in order to implement that strategy when designing a system for monitoring water quality in a river. Finally, we present and analyze the results when applying the proposed technique to study a real case in the Neuse River (North Carolina, USA).