Occurrence of PPCPs in the marine environment: a review

Little research has been conducted on the occurrence of pharmaceuticals and personal care products (PPCPs) in the marine environment despite being increasingly impacted by these contaminants. This article reviews data on the occurrence of PPCPs in seawater, sediment, and organisms in the marine environment. Data pertaining to 196 pharmaceuticals and 37 personal care products reported from more than 50 marine sites are analyzed while taking sampling strategies and analytical methods into account. Particular attention is focused on the most frequently detected substances at highest concentrations. A snapshot of the most impacted marine sites is provided by comparing the highest concentrations reported for quantified substances. The present review reveals that: (i) PPCPs are widespread in seawater, particularly at sites impacted by anthropogenic activities, and (ii) the most frequently investigated and detected molecules in seawater and sediments are antibiotics, such as erythromycin. Moreover, this review points out other PPCPs of concern, such as ultraviolet filters, and underlines the scarcity of data on those substances despite recent evidence on their occurrence in marine organisms. The exposure of marine organisms in regard to these insufficient data is discussed.     

First inter-laboratory comparison exercise for the determination of anticancer drugs in aqueous samples

The results of an inter-laboratory comparison exercise to determine cytostatic anticancer drug residues in surface water, hospital wastewater and wastewater treatment plant effluent are reported. To obtain a critical number of participants, an invitation was sent out to potential laboratories identified to have the necessary knowledge and instrumentation. Nine laboratories worldwide confirmed their participation in the exercise. The compounds selected (based on the extent of use and laboratories capabilities) included cyclophosphamide, ifosfamide, 5-fluorouracil, gemcitabine, etoposide, methotrexate and cisplatinum. Samples of spiked waste (hospital and wastewater treatment plant effluent) and surface water, and additional non-spiked hospital wastewater, were prepared by the organising laboratory (Jo?ef Stefan Institute) and sent out to each participant partner for analysis. All analytical methods included solid phase extraction (SPE) and the use of surrogate/internal standards for quantification. Chemical analysis was performed using either liquid or gas chromatography mass (MS) or tandem mass (MS/MS) spectrometry. Cisplatinum was determined using inductively coupled plasma mass spectrometry (ICP-MS). A required minimum contribution of five laboratories meant that only cyclophosphamide, ifosfamide, methotrexate and etoposide could be included in the statistical evaluation. z-score and Q test revealed 3 and 4 outliers using classical and robust approach, respectively. The smallest absolute differences between the spiked values and the measured values were observed in the surface water matrix. The highest within-laboratory repeatability was observed for methotrexate in all three matrices (CV?≤?12 %). Overall, inter-laboratory reproducibility was poor for all compounds and matrices (CV 27–143 %) with the only exception being methotrexate measured in the spiked hospital wastewater (CV?=?8 %). Random and total errors were identified by means of Youden plots.     

Biodegradability of the anticancer drug etoposide and identification of the transformation products

Etoposide susceptibility to microbiological breakdown was studied in a batch biotransformation system, in the presence or absence of artificial wastewater containing nutrients, salts and activated sludge at two concentration levels. The primary focus of the present study was to study etoposide transformation products by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry (MS/MS). Data-dependent experiments combining full-scan MS data with product ion spectra were acquired to identify the molecular ions of etoposide transformation products, to propose the molecular formulae and to elucidate their chemical structures. Due to the complexity of the matrix, visual inspection of the chromatograms showed no clear differences between the controls and the treated samples. Therefore, the software package MZmine was used to facilitate the identification of the transformation products and speed up the data analysis. In total, we propose five transformation products; among them, four are described as etoposide transformation products for the first time. Even though the chemical structures of these new compounds cannot be confirmed due to the lack of standards, their molecular formulae can be used to target them in monitoring studies.     

Source apportionment of PM2.5 for supporting control strategies in the Monterrey Metropolitan Area,Mexico

The Monterrey Metropolitan Area (MMA) in Northeast Mexico has shown high PM_2.5 concentrations since 2003. The data shows that the annual average concentration exceeds from 2 to 3 times the Mexican PM_2.5 annual air quality standard of 12 µg/m³. In a previous work we studied the chemical characterization of PM_2.5 in two sites of the MMA during the winter season. Among the most important components we found ammonium sulfate and nitrate, elemental and organic carbon, and crustal matter. In this work we present the results of a second chemical characterization study performed during the summer time and the application of the chemical mass balance (CMB) model to determine the source apportionment of air pollutants in the region. The chemical analysis results show that the chemical composition of PM_2.5 is similar in both sites and periods of the year. The results of the chemical analysis and the CMB model show that industrial, traffic, and combustion activities in the area are the major sources of primary PM_2.5 and precursor gases of secondary inorganic and organic aerosol (SO₂, NOx, NH₃, and volatile organic compounds [VOCs]). We also found that black carbon and organic carbon are important components of PM_2.5 in the MMA. These results are consistent with the MMA emission inventory that reports as major sources of particles and SO₂ a refinery and fuel combustion, as well as nitrogen oxides and ammonium from transportation and industrial activities in the MMA and ammonium form agricultural activities in the state. The results of this work are important to identify and support effective actions to reduce direct emissions of PM_2.5 and its precursor gases to improve air quality in the MMA. Implications: The Monterrey Metropolitan Area (MMA) has been classified as the most air-polluted area in Mexico by the World Health Organization (WHO). Effective actions need to be taken to control primary sources of PM_2.5 and its precursors, reducing health risks on the population exposed and their associated costs. The results of this study identify the main sources and their estimated contribution to PM_2.5 mass concentration, providing valuable information to the local environmental authorities to take decisions on PM_2.5 control strategies in the MMA.     

Nitrogen fixation by cyanobacteria stimulates production in Baltic food webs

Filamentous, nitrogen-fixing cyanobacteria form extensive summer blooms in the Baltic Sea. Their ability to fix dissolved N₂ allows cyanobacteria to circumvent the general summer nitrogen limitation, while also generating a supply of novel bioavailable nitrogen for the food web. However, the fate of the nitrogen fixed by cyanobacteria remains unresolved, as does its importance for secondary production in the Baltic Sea. Here, we synthesize recent experimental and field studies providing strong empirical evidence that cyanobacterial nitrogen is efficiently assimilated and transferred in Baltic food webs via two major pathways: directly by grazing on fresh or decaying cyanobacteria and indirectly through the uptake by other phytoplankton and microbes of bioavailable nitrogen exuded from cyanobacterial cells. This information is an essential step toward guiding nutrient management to minimize noxious blooms without overly reducing secondary production, and ultimately most probably fish production in the Baltic Sea.     

Geogenic Distribution of Arsenic (As) and Antimony (Sb) in Soils of the Murcia Region in Spain

The objective of this study was to determine the As and Sb contents in soils from the Murcia Region of Spain and the possible relationship between the mineralogical composition, soil properties, and As and Sb concentrations. In this study, 490 samples were selected from areas with different characteristics in order to study As and Sb variability. Results show that As and Sb concentrations are positively correlated with the phyllosilicate and quartz content but negatively correlated with the calcite content. The generic reference level (GRL) for these elements was determined according to the Spanish legislation. Established GRL values vary according to the established mineralogical groups, suggesting that GRL has to be determined considering the lithological characteristics of the study area.