Investigation of pharmaceutical metabolites in environmental waters by LC-MS/MS

Pharmaceuticals, once ingested, are commonly metabolized in the body into more polar and soluble forms. These compounds might not be completely removed in the wastewater treatment plants and consequently being discharged into the aquatic ecosystem. In this work, a multi-class sensitive method for the analysis of 21 compounds, including 7 widely consumed pharmaceuticals and 14 relevant metabolites, has been developed based on the use of UHPLC-MS/MS in selected reaction monitoring (SRM) mode. The method was validated in six surface waters (SW) and six effluent wastewaters (EWW) at realistic concentration levels that can be found in waters. The optimized method was applied to the analysis of different types of water samples (rivers, lakes and effluent wastewater), detecting nearly all the parent compounds and metabolites investigated in this work. This fact illustrates that not only pharmaceuticals but also their metabolites are commonly present in these types of waters. Analytical research and monitoring programs should be directed not only towards parent pharmaceuticals but also towards relevant metabolites to have a realistic overview of the impact of pharmaceuticals in the aquatic environment.     

Statistical thermodynamics of adsorption of dye DR75 onto natural materials and its modifications: double-layer model with two adsorption energies

In this article, adsorption modelling was presented to describe the sorption of textile dye, Direct Red 75 (DR75), from coloured wastewater onto the natural and modified adsorbent, Posidonia oceanica. The formulation of the double-layer model with two energy levels was based on statistical physics and theoretical considerations. Thanks to the grand canonical ensemble in statistical physics some physico-chemical parameters related to the adsorption process were introduced in the analytical model expression. Fitting results show that the dye molecules are adsorbed in parallel position to the adsorbent surface. The magnitudes of the calculated adsorption energies show that the DR75 dye is physisorbed onto Posidonia. Both Van der Waals and hydrogen interactions are implicated in the adsorption process. Despite its simplicity, the model fits a wide range of experimental data, thereby supporting the underlying data that the grafted groups facilitate the parallel anchorage of the anionic dye molecule. Thermodynamic parameters, such as adsorption energy, entropy, Gibbs free adsorption energy and internal energy were calculated according to the double-layer model. Results suggested that the DR75 adsorption onto Posidonia was a spontaneous and exothermic process.     

Identification and source apportionment of polycyclic aromatic hydrocarbons in ambient air particulate matter of Riyadh, Saudi Arabia

In an effort to assess the occurrence and sources of polycyclic aromatic hydrocarbons (PAHs) in the ambient air of Riyadh, Saudi Arabia, PM₁₀ samples were collected during December 2010. Diagnostic PAH concentration ratios were used as a tool to identify and characterize the PAH sources. The results reflect high PM₁₀ and PAH concentrations (particulate matter (PM)?=?270–1,270 μg/m³). The corresponding average PAH concentrations were in the range of 18?±?8 to 1,003?±?597 ng/m³ and the total concentrations (total PAHs (TPAHs) of 17 compounds) varied from 1,383 to 13,470 ng/m³ with an average of 5,871?±?2,830 ng/m³. The detection and quantification limits were 1–3 and 1–10 ng/ml, respectively, with a recovery range of 42–80 %. The ratio of the sum of the concentrations of the nine major non-alkylated compounds to the total (CPAHs/TPAHs) was 0.87?±?0.10, and other ratios were determined to apportion the PM sources. The PAHs found are characteristic for emissions from traffic with diesel being a predominant source.     

Comparative statistical study of hourly precipitation determined by radar-based Stage IV and ground-based methods in the North Central United States

Detailed hourly precipitation data are required for long-range modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants using the CALPUFF model. In sparsely populated areas such as the north central United States, ground-based precipitation measurement stations may be too widely spaced to offer a complete and accurate spatial representation of hourly precipitation within a modeling domain. The availability of remotely sensed precipitation data by satellite and the National Weather Service array of next-generation radars (NEXRAD) deployed nationally provide an opportunity to improve on the paucity of data for these areas. Before adopting a new method of precipitation estimation in a modeling protocol, it should be compared with the ground-based precipitation measurements, which are currently relied upon for modeling purposes. This paper presents a statistical comparison between hourly precipitation measurements for the years 2006 through 2008 at 25 ground-based stations in the north central United States and radar-based precipitation measurements available from the National Center for Environmental Predictions (NCEP) as Stage IV data at the nearest grid cell to each selected precipitation station. It was found that the statistical agreement between the two methods depends strongly on whether the ground-based hourly precipitation is measured to within 0.1 in/hr or to within 0.01 in/hr. The results of the statistical comparison indicate that it would be more accurate to use gridded Stage IV precipitation data in a gridded dispersion model for a long-range simulation, than to rely on precipitation data interpolated between widely scattered rain gauges.

Implications:

The current reliance on ground-based rain gauges for precipitation events and hourly data for modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants results in potentially large discontinuity in data coverage and the need to extrapolate data between monitoring stations. The use of radar-based precipitation data, which is available for the entire continental United States and nearby areas, would resolve these data gaps and provide a complete and accurate spatial representation of hourly precipitation within a large modeling domain.     

The amorphous Zn biomineralization at Naracauli stream,Sardinia: electron microscopy and X-ray absorption spectroscopy

An amorphous Zn biomineralization (“white mud”), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.     

Effects of environmentally relevant concentrations of metallic compounds on the flatfish Scophthalmus maximus: biomarkers of neurotoxicity,oxidative stress and metabolism

Flatfish species, such as the turbot (Scophthalmus maximus), are common targets for toxic effects, since they are exposed through the food chain (ingestion of contaminated preys) and are in direct contact with the waterborne contaminant and sediments. Furthermore, these fish species live in close proximity to interstitial water that frequently dissolves high amounts of contaminants, including metals. Despite this significant set of characteristics, the present knowledge concerning flatfish contamination and toxicity by metals is still scarce. To attain the objective of assessing the effects of metals on a flatfish species, S. maximus specimens were chronically exposed to lead, copper and zinc, at ecologically relevant concentrations, and biochemical (oxidative stress: catalase and glutathione S-transferases activities, and lipid peroxidation; neurotoxicity: cholinesterase activity) parameters were assessed on selected tissues (gills and liver). Copper had no significant effects on all tested parameters; lead was causative of significant increases in liver GSTs activities and also in lipoperoxidation of gill tissue; exposure to zinc caused a significant increase in catalase activity of gill tissue. None of the tested metals elicited noteworthy effects in terms of neurotoxicity. The obtained results showed that only the metal lead is of some environmental importance, since it was able to cause deleterious modifications of oxidative nature at relevant concentrations.     

Distribution of PCDD/Fs and dioxin-like PCBs in sediment and plants from a contaminated salt marsh (Tejo estuary,Portugal)

Concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in sediment and plants collected from a salt marsh in the Tejo estuary, Portugal. The highest PCDD/F and dl-PCB concentrations were detected in uncolonized sediments, averaging 325.25?±?57.55 pg g^?1 dry weight (dw) and 8,146.33?±?2,142.14 pg g^?1 dw, respectively. The plants Sarcocornia perennis and Halimione portulacoides growing in PCDD/F and dl-PCB contaminated sediments accumulated contaminants in roots, stems, and leaves. It was observed that PCDD/F and dl-PCB concentrations in roots were significantly lower in comparison with stems and leaves. In general, concentration of ΣPCDD/Fs and Σdl-PCBs in H. portulacoides tissues were found to be twofold higher than those in S. perennis, indicating a difference in the accumulation capability of both species. Furthermore, congener profiles changed between sediments and plant tissues, reflecting a selective accumulation of low chlorinated PCDD/Fs and non-ortho dl-PCBs in plants.     

Predicting Satisfaction with Smart Irrigation Controllers and Their Long‐Term Use among Homeowners in Central Florida

Studies throughout Florida have shown smart controllers can substantially reduce irrigation under residential high‐water use conditions. However, successful promotion requires understanding the link between controller performance and the mechanisms by which they are adopted. This article compares irrigation water‐use and survey data collected from households installed with soil moisture sensor and evapotranspiration controllers. The study investigated whether the relative change in irrigation use between two years preceding and two years following installation was a reliable predictor of a homeowner's satisfaction with the device and likelihood of continuing to use it. Results indicated relative changes in irrigation use were only significantly associated with the quality of controller programming. Satisfaction with the controller was largely attributable to satisfaction with the appearance of the landscape and the perceived water‐saving effectiveness of the controller whereas the likelihood of its continued use was only significantly predicted by the level of technical knowledge regarding its functioning and whether or not challenges were experienced with it. Targeting homeowners with supplemental user‐friendly information may best support their long‐term adoption of smart controllers while providing irrigation contractors with training in implementation techniques would represent an integrated strategy for added reductions in residential outdoor water use.     

GC estimation of organic hydrocarbons that threaten shallow Quaternary sandy aquifer Northwestern Gulf of Suez,Egypt

Soil and groundwater contamination is one of the important environmental problems at petroleum-related sites, which causes critical environmental and health defects. Severe petroleum hydrocarbon contamination from coastal refinery plant was detected in a shallow Quaternary sandy aquifer is bordered by Gulf in the Northwestern Gulf of Suez, Egypt. The overall objective of this investigation is to estimate the organic hydrocarbons in shallow sandy aquifers, released from continuous major point-source of pollution over a long period of time (91 years ago). This oil refinery contamination resulted mainly in the improper disposal of hydrocarbons and produced water releases caused by equipment failures, vandalism, and accidents that caused direct groundwater pollution or discharge into the gulf. In order to determine the fate of hydrocarbons, detailed field investigations were made to provide intensive deep profile information. Eight composite randomly sediment samples from a test plot were selected for demonstration. The tested plot was 50 m long?×?50 m wide?×?70 cm deep. Sediment samples were collected using an American auger around the point 29° 57′ 33″ N and 32° 30′ 40″ E in 2012 and covered an area of 2,500 m² which represents nearly 1/15 of total plant area (the total area of the plant is approximately 3.250 km²). The detected total petroleum hydrocarbons (TPHs) were 2.44, 2.62, 4.54, 4.78, 2.83, 3.22, 2.56, and 3.13 wt%, respectively. TPH was calculated by differences in weight and subjected to gas chromatography (GC). Hydrocarbons were analyzed on Hewlett–Packard (HP-7890 plus) gas chromatograph equipped with a flame ionization detector (FID). The percentage of paraffine of the investigated TPH samples was 7.33, 7.24, 7.58, 8.25, 10.25, 9.89, 14.77, and 17.53 wt%, respectively.