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.     

Emission factors from different burning stages of agriculture wastes in Mexico

Open-air burning of agricultural wastes from crops like corn, rice, sorghum, sugar cane, and wheat is common practice in Mexico, which in spite limiting regulations, is the method to eliminate such wastes, to clear the land for further harvesting, to control grasses, weeds, insects, and pests, and to facilitate nutrient absorption. However, this practice generates air pollution and contributes to the greenhouse effect. Burning of straws derived from the said crops was emulated in a controlled combustion chamber, hence determining emission factors for particles, black carbon, carbon dioxide, carbon monoxide, and nitric oxide throughout the process, which comprised three apparent stages: pre-ignition, flaming, and smoldering. In all cases, maximum particle concentrations were observed during the flaming stage, although the maximum final contributions to the particle emission factors corresponded to the smoldering stage. The comparison between particle size distributions (from laser spectrometer) and black carbon (from an aethalometer) confirmed that finest particles were emitted mainly during the flaming stage. Carbon dioxide emissions were also highest during the flaming stage whereas those of carbon monoxide were highest during the smoldering stage. Comparing the emission factors for each straw type with their chemical analyses (elemental, proximate, and biochemical), some correlations were found between lignin content and particle emissions and either particle emissions or duration of the pre-ignition stage. High ash or lignin containing-straw slowed down the pre-ignition and flaming stages, thus favoring CO oxidation to CO₂.

     

Developmental toxicity of PAH mixtures in fish early life stages. Part II: adverse effects in Japanese medaka

In aquatic environments, polycyclic aromatic hydrocarbons (PAHs) mostly occur as complex mixtures, for which risk assessment remains problematic. To better understand the effects of PAH mixture toxicity on fish early life stages, this study compared the developmental toxicity of three PAH complex mixtures. These mixtures were extracted from a PAH-contaminated sediment (Seine estuary, France) and two oils (Arabian Light and Erika). For each fraction, artificial sediment was spiked at three different environmental concentrations roughly equivalent to 0.5, 4, and 10 μg total PAH g^?1 dw. Japanese medaka embryos were incubated on these PAH-spiked sediments throughout their development, right up until hatching. Several endpoints were recorded at different developmental stages, including acute endpoints, morphological abnormalities, larvae locomotion, and genotoxicity (comet and micronucleus assays). The three PAH fractions delayed hatching, induced developmental abnormalities, disrupted larvae swimming activity, and damaged DNA at environmental concentrations. Differences in toxicity levels, likely related to differences in PAH proportions, were highlighted between fractions. The Arabian Light and Erika petrogenic fractions, containing a high proportion of alkylated PAHs and low molecular weight PAHs, were more toxic to Japanese medaka early life stages than the pyrolytic fraction. This was not supported by the toxic equivalency approach, which appeared unsuitable for assessing the toxicity of the three PAH fractions to fish early life stages. This study highlights the potential risks posed by environmental mixtures of alkylated and low molecular weight PAHs to early stages of fish development.     

Foraminiferal biotopes and their distribution control in Ria de Aveiro (Portugal): a multiproxy approach

Ria de Aveiro, which is located in the centre of Portugal (40° 38′ N, 8° 45′ W), is a well-mixed and complex coastal lagoon that is separated from the sea by a sandy barrier and connects with the Atlantic through an artificial inlet. Tidal currents are the main factor controlling the lagoon’s hydrodynamics and, to a great extent, the sedimentary dynamic. The inner lagoonal zones receive input from several rivers and experience the pressure caused by the accumulation of organic matter and pollutants (namely, trace metals) from diverse anthropic activities. This paper is the first piece of work aiming to recognize, characterize and explain the main benthic foraminiferal biotopes in Ria de Aveiro. To provide a broad overview of this kind of setting, our results are compared to those of previous published studies conducted in similar transitional environments. The research is based on an investigation of 225 sites spread throughout this ecosystem. Utilizing a statistical approach, this study analyses the details of dead benthic foraminiferal assemblages composed of 260 taxa, the texture and composition (mineralogical and geochemical) of the sediment and physicochemical data. On the basis of the results of R-mode and Q-mode cluster analyses, several different biotopes can be defined as marsh biotope/near-marsh biotope; marginal urban/marginal urban mixing biotope; inner-outer lagoon biotope or enclosed lagoon; outer lagoon biotope, mixed sub-biotope; and outer lagoon, marine sub-biotope. These biotopes are related to foraminifera assemblages and substrate type and are influenced by local currents, water depth, chemical and physicochemical conditions, river or oceanic proximity, and anthropogenic impact, as evidenced by the mapping of the six factor loadings of the principal component analysis conducted herein. Based on a similar methodology of analysis as that applied in previous studies in the Lagoon of Venice, comparable biotypes were identified in Lagoon of Aveiro.     

Design of water quality monitoring networks with two information scenarios in tropical Andean basins

Design and redesign of water quality monitoring networks were evaluated for two similarly sized watersheds in the tropical Andes via optimization techniques using geographic information system technology (GIS) and a matter-element analysis of 5-day biological oxygen demand (BOD₅) and total suspended solids (TSS). This resulted in a flexible, objectively based design for a 1128-km² watershed without prior water quality data (La Miel River), and a network redesign of a 1052-km² watershed with historical water quality monitoring (Chinchiná River). Monitoring design for the undocumented basin incorporated mathematical expressions for physical, anthropological, and historical factors—and was based on clear objectives for diagnosis and intervention of water pollution. Network redesign identified network redundancy, which resulted in a 64% reduction in the number of water quality monitoring stations along the channel, and a 78% reduction of stations throughout the basin. Most tropical drainage basins throughout the world have little to no prior water quality data. But even in well-studied drainage basins like the Chinchiná River, which is among the most thoroughly studied basins in Colombia, redesign of historical and existing monitoring networks will become a standard tool to advance the restoration of polluted surface waters, not only in Colombia, but also throughout the world.     

Trace elements in muscle of three fish species from Todos os Santos Bay,Bahia State,Brazil

In this study, an analysis was performed on the concentrations of the trace elements Al, As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn in muscle of two carnivorous and one planktivorous fish species collected at Todos os Santos Bay (BTS). The accumulation order of the trace elements in Lutjanus analis was Al >Zn >Fe >Cr >Ba >Ni. In Cetengraulis edentulus, the order was Al >Fe >Zn >Cr >Ni >Mn >As. In the species Diapterus rhombeus, the order was Al >Fe >Zn >Cr >Ni >Mn >Cd. To determine the risk related to the consumption of fish, toxicity guidelines were used as standard references. It was observed that the species C. edentulus contained concentrations of As exceeding WHO limits, but these concentrations were acceptable according to the Agência Nacional de Vigilância Sanitária (ANVISA) guidelines. Cd levels were found only in D. rhombeus and in low concentrations according to the determinations of WHO and ANVISA. Pb levels were not detected in any of the three fish species. The analyzed elements did not differ statistically according to the species and feeding habits. The results point to possible risks of human contamination by As related to the consumption of the fish species C. edentulus from the BTS.     

Mechanical and toxicological evaluation of concrete artifacts containing waste foundry sand

The creation of metal parts via casting uses molds that are generally made from sand and phenolic resin. The waste generated after the casting process is called waste foundry sand (WFS). Depending on the mold composition and the casting process, WFS can contain substances that prevent its direct emission to the environment. In Brazil, this waste is classified according to the Standard ABNT NBR 10004:2004 as a waste Class II (Non-Inert). The recycling of this waste is limited because its characteristics change significantly after use. Although the use (or reuse) of this byproduct in civil construction is a technically feasible alternative, its effects must be evaluated, especially from mechanical and environmental points of view. Thus, the objective of this study is to investigate the effect of the use of WFS in the manufacture of cement artifacts, such as masonry blocks for walls, structural masonry blocks, and paving blocks. Blocks containing different concentrations of WFS (up to 75% by weight) were produced and evaluated using compressive strength tests (35 MPa at 28 days) and toxicity tests on Daphnia magna, Allium cepa (onion root), and Eisenia foetida (earthworm). The results showed that there was not a considerable reduction in the compressive strength, with values of 35 ± 2 MPa at 28 days. The toxicity study with the material obtained from leaching did not significantly interfere with the development of D. magna and E. foetida, but the growth of the A. cepa species was reduced. The study showed that the use of this waste in the production of concrete blocks is feasible from both mechanical and environmental points of view.     

Sediments as a sink for UV filters and benzotriazoles: the case study of Upper Iguaçu watershed,Curitiba (Brazil)

Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g⁻¹ dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.

     

Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.     

Epiphyte toxicity bioassay for ecotoxicological and coastal monitoring

Marine epibionts are organisms that grow on submerged surfaces. Those found on seagrass leaves are especially important because of their interactions with the plants, their contribution to primary production in these ecosystems, and their role as food source for heterotrophic fauna. Given the relative lack of ecotoxicological studies on epibionts, the aim of this study is to evaluate the effect of environmental pollution on epiphytes experimentally attached to artificial devices (mimes) consisting of thermally-sealed silicone tubes supported on bamboo sticks that mimic the morphology of seagrasses and serve as an anchor surface for marine epibionts. Mimes were installed on the sea floor in subtidal waters of the Rio San Pedro (Cádiz), collected after 28 days, and incubated in the laboratory with environmental concentrations of atrazine (herbicide), Irgarol (anti-fouling substance), and copper. Tube-dwelling diatoms formed the major component of the epiphyte community. Average surface covering, chlorophyll, and biomass content did not show significant differences between controls and treatments. The glutathione peroxidase activity increased significantly with 4 μg L^?1 of atrazine and 5 μg L^?1 of copper. This enzymatic activity increase seems to be sufficient to prevent oxidative cellular damage by removing reactive oxygen substances produced by oxidative stress; in addition to this enzyme, there might be other antioxidant enzymes which have not been measured in this study, that have also protected the organism from oxidative damage. Thus, the measurement of antioxidant enzymatic activity in epiphytes may be a useful toxicity indicator for coastal biomonitoring.