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.     

Effect of ibuprofen exposure on blood,gill, liver,and brain on common carp (Cyprinus carpio) using oxidative stress biomarkers

Although trace concentrations of ibuprofen (IBP) have been detected in diverse water bodies, there is currently insufficient information on the potentially deleterious effects of this xenobiotic. The present study aimed to determine whether IBP induces oxidative stress in brain, liver, gill, and blood of the common carp Cyprinus carpio. To this end, the median lethal concentration at 96 h (96-h LC₅₀) was determined and the lowest observed adverse effect level was established. Carp were exposed to the latter concentration (17.6 mg L^?1) for 12, 24, 48, 72, and 96 h, and the following biomarkers were evaluated: lipid peroxidation (LPX) and activity of the antioxidant enzymes superoxide dismutase, catalase, and glutathione peroxidase. Results indicated that LPX and antioxidant enzymes’ activity increased significantly (p?<?0.05) with respect to the control group in liver, gill, and blood, while no significant differences occurred in brain. In conclusion, IBP induced oxidative stress on C. carpio, the liver being the organ most affected by this damage.     

Distribution and ecological risk of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in surface sediments from the Bizerte lagoon,Tunisia

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were determined in 18 surface sediment samples collected from Bizerte lagoon, Tunisia. The total concentrations of ten PCBs (∑PCBs) and of four OCPs (∑OCPs) in the sediments from this area ranged from 0.8 to 14.6 ng g^?1 dw (average value, 3.9 ng g^?1 dw) and from 1.1 to 14.0 ng g^?1 dw (average value, 3.3 ng g^?1 dw), respectively. Among the OCPs, the range of concentrations of dichlorodiphenyltrichloroethane and its metabolites (DDTs) and hexachlorobenzene (HCB) were 0.3–11.5 ng g^?1 dw (1.9 ng g^?1 dw) and 0.6–2.5 ng g^?1 dw (1.4 ng g^?1 dw), respectively. Compositional analyses of the POPs indicated that PCB 153, 138 and 180 were the predominant congeners accounting for 60 % of the total PCBs. In addition, p,p′-DDT was found to be the dominant DDTs, demonstrating recent inputs in the environment. Compared with some other regions of the world, the Bizerte lagoon exhibited low levels of PCBs and moderate levels of HCB and DDTs. The high ratios ΣPCBs/ΣDDTs indicated predominant industrial versus agricultural activities in this area. According to the established guidelines for sediment quality, the risk of adverse biological effects from such levels of OCPs and PCBs, as recorded at most of the study sites, was insignificant. However, the higher concentrations in stations S1 and S3 could cause biological damage.     

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.     

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments

The study describes the environmental monitoring of anionic surfactants―alcohol sulfates (AS) and alcohol ethoxysulfates (AES)—in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry analysis (LC–MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg^?1 for AS, from 3.04 to 10.68 mg kg^?1 for AES–C₁₂E_x and from 3.83 to 11.56 mg kg^?1 for AES–C₁₄E_x.     

Optimization-Based Atmospheric Plume Source Identification

This work applies optimization and an Eulerian inversion approach presented by Bagtzoglou and Baun in 2005 in order to reconstruct contaminant plume time histories and to identify the likely source of atmospheric contamination using data from a real test site for the first time. Present-day distribution of an atmospheric contaminant plume as well as data points reflecting the plume history allow the reconstruction and provide the plume velocity, distribution, and probable source. The method was tested to a hypothetical case and with data from the Forest Atmosphere Transfer and Storage (FACTS) experiment in the Duke experimental forest site. In the scenarios presented herein, as well as in numerous cases tested for verification purposes, the model conserved mass, successfully located the peak of the plume, and managed to capture the motion of the plume well but underestimated the contaminant peak.     

Use of Revised Universal Soil Loss Equation (RUSLE) and Historical Imagery for Claims of Sedimentation of Lakes and Streams

The consequences of erosion and subsequent sedimentation of lakes and streams are many and widespread. The natural process of erosion can be accelerated by land cover changes with an increase in areas of impervious surfaces. Sediment is continually being transported along all streams in nature and can come from anywhere in the watershed. Lakes slow the rate of velocity of the water and allow the entrained sediment to settle and accumulate. When sediment impacts water impoundments, legal actions may result. Even with evidence of specific sediment release, the forensic analysis may not be an open-and-shut case. The author presents a method to investigate the validity of a legal claim of a sediment-impacted lake at the outfall of a mixed rural/urban watershed. By combining land use change, soils, elevation and precipitation data, a maximum possible annual sediment loss was approximately 154 tonne per hectare (15.4 kg/m²). Lacking evidence of specific historic events of erosion and subsequent sedimentation, this method provides an equitable means of determining compensatory damages. Using aerial and satellite imagery provided historical evidence of land cover change and examples of significant erosion in the watershed and not named in the lawsuit. The focus of the litigation started with the property adjoining the effected lake. The analysis provides a method to investigate erosion and subsequent sedimentation claims at a watershed-scale.     

Present and future climate resources for various types of tourism in the Bay of Palma,Spain

The Bay of Palma, in Mallorca, is a leading region for beach holidays in Europe. It is based on a mass tourism model strongly modulated by seasonality and with high environmental costs. Main tourism stakeholders are currently implementing complementary activities to mitigate seasonality, regardless of climate change. But climate is—and will remain—a key resource or even a limitation for many types of tourism. Assessing the present conditions and exploring the future evolution of climate potential for these activities have become a priority in this area. To this end, the climate index for tourism (CIT)—originally designed to rate the climate resource of beach tourism—is adapted to specifically appraise cycling, cultural tourism, football, golf, motor boating, sailing and hiking. Climate resources are derived by using observed and projected daily meteorological data. Projections have been obtained from a suite of Regional Climate Models run under the A1B emissions scenario. To properly derive CITs at such local scale, we apply a statistical adjustment. Present climate potentials ratify the appropriateness of the Bay of Palma for satisfactorily practicing all the examined activities. However, optimal conditions are projected to degrade during the peak visitation period while improving in spring and autumn. That is, climate change could further exacerbate the present imbalance between the seasonal distributions of ideal climate potentials and high attendance levels. With this information at hand, policy makers and regional tourism stakeholders can respond more effectively to the great challenge of local adaptation to climate change.     

Looking beyond the average agricultural impacts in defining adaptation needs in Europe

The effects of climate change on agriculture are often characterised by changes in the average productivity of crops; however, these indicators provide limited information regarding the risks associated with fluctuations in productivity resulting from future changes in climate variability that may also affect agriculture. In this context, this study evaluates the combined effects of the risks associated with anomalies reflected by changes in the mean crop yield and the variability of productivity in European agro-climatic regions under future climate change scenarios. The objective of this study is to evaluate adaptation needs and to identify regional effects that should be addressed with greater urgency in the light of the risks and opportunities that are identified. The results show differential effects on regional agriculture and highlight the importance of considering both regional average impacts and the variability in crop productivity in setting priorities for the adaptation and maintenance of rural incomes and agricultural insurance programmes.     

Adaptation options for marine industries and coastal communities using community structure and dynamics

Identifying effective adaptation strategies for coastal communities dependent on marine resources and impacted by climate change can be difficult due to the dynamic nature of marine ecosystems. The task is more difficult if current and predicted shifts in social and economic trends are considered. Information about social and economic change is often limited to qualitative data. A combination of qualitative and quantitative models provide the flexibility to allow the assessment of current and future ecological and socio-economic risks and can provide information on alternative adaptations. Here, we demonstrate how stakeholder input, qualitative models and Bayesian belief networks (BBNs) can provide semi-quantitative predictions, including uncertainty levels, for the assessment of climate and non-climate-driven change in a case study community. Issues are identified, including the need to increase the capacity of the community to cope with change. Adaptation strategies are identified that alter positive feedback cycles contributing to a continued decline in population, local employment and retail spending. For instance, the diversification of employment opportunities and the attraction of new residents of different ages would be beneficial in preventing further population decline. Some impacts of climate change can be combated through recreational bag or size limits and monitoring of popular range-shifted species that are currently unmanaged, to reduce the potential for excessive removal. Our results also demonstrate that combining BBNs and qualitative models can assist with the effective communication of information between stakeholders and researchers. Furthermore, the combination of techniques provides a dynamic, learning-based, semi-quantitative approach for the assessment of climate and socio-economic impacts and the identification of potential adaptation strategies.