Biodegradability and transformation of human pharmaceutical active ingredients in environmentally relevant test systems

Human pharmaceutical active ingredients that are orally or parenterally administered may be metabolised in the body and after excretion may be further transformed in the receiving environmental compartments. The optimal outcome from an environmental point of view—complete mineralisation—is rarely observed. Small molecule pharmaceuticals are commonly not readily biodegradable according to Organisation for Economic Cooperation and Development (OECD) 301 tests. However, primary transformation is often observed. To gain information on the transformation of active ingredients in the environment, long-term studies like transformation in aquatic water/sediment systems according to OECD guideline 308 are required for the environmental risk assessment for human active pharmaceutical ingredients. Studies received until mid 2010 as part of the dossiers for marketing authorisation applications were evaluated concerning transformation products. The evaluation revealed that in 70 % of the studies, at least one transformation product (TP) is formed above 10 % of the originally applied dose, but in only 26 % of the studies are all TP identified. The evaluation also revealed that some TP of pharmaceutical active ingredients show a considerably longer DT₅₀ compared to the parent compound. An example is the TP (val)sartan acid that is formed from an antihypertensive compound.     

Effect of water composition on the photocatalytic removal of pesticides with different TiO2 catalysts

The objective of this work is double—firstly to explore the photocatalytic efficiency of five different commercial TiO₂ catalysts in the photodegradation of a mixture of pesticides classified by the EU as priority pollutants and secondly to analyze the correlation between their physicochemical properties and the inhibition of the studied photocatalytic process when natural water was employed. Photocatalytic efficiencies when ultrapure water was used seem to point out that surface area was not a prerequisite for the photodegradation of the selected mixture of pesticides. On the other hand, significant differences in total organic carbon (TOC) conversions were obtained with the two studied water compositions. On one side, Evonik materials appear to be mostly inhibited when natural water was employed, whereas on the other, it should be remarked that anatase Sigma-Aldrich (SA) and, particularly, Hombikat UV100 (HBK) materials presented a very limited photo-efficiency inhibition or even a higher initial rate of TOC removal when a natural water matrix was used, probably due to their specific surface properties (PZC, S _BET). Therefore, heterogeneous photocatalysis has proved to be a promising technology for the degradation of the selected mixture of pesticides where the final photo-efficiency of the five commercial titania catalysts studied here responds to a complex balance between its surface and structural properties.     

Obtaining polycyclic aromatic hydrocarbon concentration ratios and molecular markers for residential wood combustion: Temuco, a case study

It is known that residential wood combustion (RWC) is an important source of fine particle emissions. The purpose of this work was to characterize the chemical composition of the particulate matter present in the Temuco urban atmosphere during winter, specifically the polycyclic aromatic hydrocarbon (PAH) profile, because PAHs are considered to be among the key compounds in particulate matter toxicity. During the 2008 winter monitoring campaign, samples of particulate matter with aerodynamic diameters of < or = 10 (PM10) and < or = 2.5 (PM2.5) microm were taken on days with contamination episodes. Sixteen U.S. Environmental Protection Agency (EPA) PAH compounds were extracted with toluene and determined by gas chromatography-mass spectrometry (GC-MS). The results show that phenantrene was the predominant compound associated with particulate matter at a concentration range between 300 and 600 ng m(-3), 18 times higher than the second most abundant PAH compound. High-molecular-mass compounds such as dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3,c,d]pyrene were also found, but they were minorities in the set. It was recognized from the PAH concentration ratios of the Temuco atmospheric aerosol that the main contamination source was in fact residential wood combustion; although not all the concentration ratios evaluated match the reported reference values, probably due to the kind of biomass used, the characteristics of Chilean heating appliances and climate.     

Effects of walnut husk washing waters and their phenolic constituents on horticultural species

INTRODUCTION: The reuse of wastewaters for agricultural purposes is a common practice in many countries and is increasingly recommended by organizations that promote sustainable development. Yet, it is restricted by the potential negative impact of these materials on soil and crops. The aim of this study was therefore to evaluate the environmental impact of walnut husk washing waters (WHWW) and their organic fractions, in order to conceive their agricultural exploitation. DISCUSSION: Phytotoxicity tests and morphological investigations on representative plant species of horticultural interest indicated that WHWW and their organic fractions can elicit a concentration-dependent stimulating effect on the growth of radish, lettuce cv. cavolo Napoli with effects up to 165 %. An opposite inhibitory effect up to 70 % was observed on spinach and lettuce cv. Gentilina. Proapoptotic effects were observed by acridine orange/ethidium bromide assay in the species inhibited by WHWW treatment. High-performance liquid chromatography-mass spectrometry analysis of the WHWW revealed the presence of a main component which was extracted selectively in organic solvents and purified by preparative chromatography. Complete spectral analysis allowed identification as 4,8-dihydroxy-1-tetralone, commonly known as regiolone. Regiolone exhibited the same concentration-dependent activity on root elongation with a stimulation in the case of radish up to 135 % with respect to control. These results open perspectives in the exploitation of WHWW and the main phenolic constituent readily available by a straightforward isolation procedure as a natural fertilizer for specific crops.     

‘End to end’ planktonic trophic web and its implications for the mussel farms in the Mar Piccolo of Taranto (Ionian Sea,Italy)

The Mar Piccolo is a semi-enclosed basin subject to different natural and anthropogenic stressors. In order to better understand plankton dynamics and preferential carbon pathways within the planktonic trophic web, an integrated approach was adopted for the first time by examining all trophic levels (virioplankton, the heterotrophic and phototrophic fractions of pico-, nano- and microplankton, as well as mesozooplankton). Plankton abundance and biomass were investigated during four surveys in the period 2013–2014. Beside unveiling the dynamics of different plankton groups in the Mar Piccolo, the study revealed that high portion of the plankton carbon (C) pool was constituted by small-sized (<2 μm) planktonic fractions. The prevalence of small-sized species within micro- and mesozooplankton communities was observed as well. The succession of planktonic communities was clearly driven by the seasonality, i.e. by the nutrient availability and physical features of the water column. Our hypothesis is that beside the ‘bottom-up’ control and the grazing pressure, inferred from the C pools of different plankton groups, the presence of mussel farms in the Mar Piccolo exerts a profound impact on plankton communities, not only due to the important sequestration of the plankton biomass but also by strongly influencing its structure.     

Ultrasensitive determination of carbendazim in water and orange juice using a carbon paste electrode

A carbon paste electrode was used for the electrochemical quantification of carbendazim in water and orange juice samples. Carbendazim oxidation on the electrode surface was found to be controlled by adsorption. The novel electrochemical procedure for carbendazim quantification employed differential pulse voltammetry using a carbon paste electrode under optimal conditions. Carbendazim oxidation currents were linear at concentrations of 2.84 to 45.44 µg L^?1, with a limit of detection of 0.96 µg L^?1. The proposed method was applied to carbendazim quantification in ultrapurified water, river water, and orange juice. Recovery rates in water and orange juice samples were in the 97%–101% range, indicating that the method can be employed to determine carbendazim in these matrices, with advantages including shorter analysis time and lower cost than routine methods such as chromatography or spectroscopy. The electrode showed good reproducibility, remarkable stability, and especially good surface renewability by simple mechanical polishing. The recovery rates observed were highly concordant with those obtained for high-performance liquid chromatography, having a relative standard deviation of less than 1.3%.     

Environmental quality assessment of reservoirs impacted by Hg from chlor-alkali technologies: case study of a recovery

Mercury (Hg) pollution legacy of chlor-alkali plants will be an important issue in the next decades with the planned phase out of Hg-based electrodes by 2025 within the Minamata convention. In such a context, the present study aimed to examine the extent of Hg contamination in the reservoirs surrounding the Oltchim plant and to evaluate the possible improvement of the environmental quality since the closure of its chlor-alkali unit. This plant is the largest chlor-alkali plant in Romania, which partly switched to Hg-free technology in 1999 and definitely stopped the use of Hg electrolysis in May 2012. Total Hg (THg) and methylmercury (CH₃Hg) concentrations were found to decrease in the surface waters and sediments of the reservoirs receiving the effluents of the chlor-alkali platform since the closure of Hg units. Hence, calculated risk quotients (RQ) indicated no adverse effect of Hg for aquatic organisms from the ambient water exposure. RQ of Hg in sediments were mostly all higher than 1, showing important risks for benthic organisms. However, ecotoxicity testing of water and sediments suggest possible impact of other contaminants and their mixtures. Hg hotspots were found in soils around the platform with RQ values much higher than 1. Finally, THg and CH₃Hg concentrations in fish were below the food safety limit set by the WHO, which contrasts with previous measurements made in 2007 revealing that 92 % of the studied fish were of high risk of consumption. Discontinuing the use of Hg electrodes greatly improved the surrounding environment of chlor-alkali plants within the following years and led to the decrease environmental exposure to Hg through fish consumption. However, sediment and soil still remained highly contaminated and problematic for the river reservoir management. The results of this ecological risk assessment study have important implications for the evaluation of the benefits as well as limits of the Minamata Convention implementation.

     

Environmental information sharing: a means to support the legitimization of oyster farmers’ stewardship over water quality management in NSW,Australia

Oyster farmers depend on good water quality. Activities upstream from estuaries result in externalities that impact water quality. Over the last 10 years, oyster farmers have been developing estuary‐wide environmental management systems ( EMSs ) to tackle internal (i.e. industry‐related) and external (i.e. catchment) issues in N ew S outh W ales, A ustralia. Drawing on interview‐based research and document analyses, this paper shows that the process of creating an EMS for the oyster industry, as well as the creation of the EMS itself, resulted in legitimizing the industry's stewardship over the natural resource it depends on (water). For the oyster industry, this result was due to a change in the scale on which EMSs have been developed: instead of viewing issues at the individual business level, the systems expanded their viewpoint to the entire catchment, and included every oyster business in the estuary, as well as all other activities in the upper catchment. By providing a means of communicating internal efforts and with the support of local government bodies, EMSs provided a mechanism with which influence over upstream actors and activities could be exerted. We demonstrate this by using the ‘social‐ecological systems’ and ‘ ENCORE ’ frameworks, emphasizing the transitions that allowed for this change of scale to take place.