Occurrence of cyclophosphamide and epirubicin in wastewaters by direct injection analysis–liquid chromatography–high-resolution mass spectrometry

Background, aim, and scope

According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography?Chigh-resolution mass spectrometry (LC?COrbitrap?CMS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents.

Materials and methods

Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200?mg hydrophilic?Clipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP.

Results and discussion

Cyclophosphamide and epirubicin were recovered after 50?mL preconcentration on solid-phase extraction 200?mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500?mL of water. Limits of detection were of 0.35 and 2.77?ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1???g/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85?ng?L^?1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8???g?L^?1.

Conclusions

The results obtained in this study demonstrate the capability of LC?COrbitrap?CMS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.     

Analysis of tropospheric ozone concentration on a Western Mediterranean site: Castellon (Spain)

Ozone dynamics in our study area (Castellon, Spain) is both strongly bound to the mesoscale circulations that develop under the effect of high insolation (especially in summer) and conditioned by the morphological characteristics of the Western Mediterranean Basin. In this work we present a preliminary analysis of ozone time series on five locations in Castellon for the period 1997–2003. We study their temporal and spatial variations at different scales: daily, weekly, seasonally and interannually. Because both the O₃ concentration and its temporal variation depend on the topographic location of the observing station, they can show large differences within tens of kilometer. We also contrast the variation in the ozone concentration with the variations found for meteorological variables such as radiation, temperature, relative humidity and recirculation of the air mass. The link between elevated ozone concentrations and high values of the recirculation factor (r=0.7–0.9) shown the importance of recirculating flows on the local air pollution episodes.     

Effects of teflubenzuron on sediment processing by members of the Capitella species-complex

The cosmopolitan deposit-feeding polychaete Capitella is widely used as an indicator of organic pollution and plays an important role in waste recycling at aquaculture sites. Teflubenzuron is currently employed by salmon farms as an in-feed compound to control ectoparasite infestations. Its occurrence in sediments could pose a hazard to local sediment infauna. A bioassay to investigate the effects of exposing Capitella sp I and Capitella sp B to sediment spiked with environmentally relevant concentrations of teflubenzuron (8.4, 25 and 41.8 microg/g dry wt. sediment) is described. No mortality was recorded for Capitella sp I, but increasing teflubenzuron concentrations significantly reduced egestion rates. Capitella sp B exhibited mortality, although egestion was not affected. These results using Capitella spp. indicated that teflubenzuron could affect the rate of sediment processing by polychaetes close to fish farms treated with this compound. Further studies are recommended to assess the potential of contaminants in aquaculture wastes.     

PM10 and PM2.5 source apportionment in the Barcelona Metropolitan area, Catalonia, Spain

Levels of total suspended particles, PM10, PM2.5 and PM1 were continuously monitored at an urban kerbside in the Metropolitan area of Barcelona from June 1999 to June 2000. The results show that hourly levels of PM2.5 and PM1 are consistent with the daily cycle of gaseous pollutants emitted by traffic, whereas TSP and PM10 do not follow the same trend, at least in the diurnal period. The PM2.5/PM10 ratio is dependent on the traffic emissions, whereas additional contribution sources for the >10 μm fraction must be taken into account in the diurnal period. Different PM10 and PM2.5 source apportionment techniques were compared. A methodology based on the chemical determination of 83% of both PM10 and PM2.5 masses allowed us to quantify the marine (4% in PM10 and <1% in PM2.5), crustal (26% in PM10 and 8% in PM2.5) and anthropogenic (54% in PM10 and 73% in PM2.5) loads. Peaks of crustal contribution to PM10 (up to 44% of the PM10 mass) were recorded under Saharan air mass intrusions. A different seasonal trend was observed for levels of sulphate and nitrate, probably as a consequence of the different thermodynamic behaviour of these PM species and the higher summer oxidation rate of SO₂.     

In utero and post-natal accumulation of organochlorine compounds in children under different environmental conditions

A study of intake of organochlorine compounds (OCs) in children both in utero and at the age of four years has been performed in two cohorts. One encompasses children born in Menorca Island between 1997 and 1998, and the other those born between 1997-1999 in Ribera d'Ebre, an in-land industrial-agricultural area of Catalonia. Comparison of the OC concentrations in serum samples from both populations, including those obtained from cord blood and blood collected at four years, provides information on the influence of local pollution sources in the accumulation of these compounds. Statistically significant differences (p < 0.01) have been found for hexachlorobenzene, indicating that chronic airborne contamination to this compound in Ribera d'Ebre involved higher in utero exposure, which increased in the first four years of growth. Similarly, in the cohort of Menorca, higher in utero exposure to PCBs was observed and this increased subsequently in the first four years of growth. Other compounds encompassing temporal contamination episodes such as gamma-HCH involved higher in utero exposure but strongly diminished in the first four years of growth. Overall, it can be concluded that local chronic pollution by OCs has a direct effect in children living in the surrounding areas. This influence is reflected in higher exposure, both in utero and in the first years of growth, that significantly stands out over the background contamination due to the ubiquity of these compounds.     

Environmental strategy and performance in small firms: a resource-based perspective

In spite of the widespread recognition of the important roles that small and medium sized enterprises (SMEs) play in most economies, limited research has focused on their impacts on the natural environment and the strategies such enterprises adopt to reduce these impacts. It is usually assumed that SMEs lack the resources to implement proactive environmental strategies that go beyond minimum regulatory compliance. In this study of 108 SMEs in the automotive repair sector in Southern Spain, we found that SMEs undertake a range of environmental strategies from reactive regulatory compliance to proactive pollution prevention and environmental leadership. These strategies are associated with three organizational capabilities: shared vision, stakeholder management, and strategic proactivity, hypothesized based on the unique strategic characteristics of SMEs--shorter lines of communication and closer interaction within the SMEs, the presence of a founder's vision, flexibility in managing external relationships, and an entrepreneurial orientation. We also found that firms with the most proactive practices exhibited a significantly positive financial performance.     

Application of compost of two-phase olive mill waste on olive grove: Effects on soil,olive fruit and olive oil quality

Composting is a method for preparing organic fertilizers that represents a suitable management option for the recycling of two-phase olive mill waste (TPOMW) in agriculture. Four different composts were prepared by mixing TPOMW with different agro-industrial by-products (olive pruning, sheep manure and horse manure), which were used either as bulking agents or as N sources. The mature composts were added during six consecutive years to a typical “Picual” olive tree grove in the Jaén province (Spain). The effects of compost addition on soil characteristics, crop yield and nutritional status and also the quality of the olive oil were evaluated at the end of the experiment and compared to a control treated only with mineral fertilization. The most important effects on soil characteristics included a significant increase in the availability of N, P, K and an increase of soil organic matter content. The application of TPOMW compost produced a significant increase in olive oil content in the fruit. The compost amended plots had a 15% higher olive oil content than those treatment with inorganic fertilization. These organics amendments maintained the composition and quality of the olive oil.     

CH4 continuous measurements in the upper Spanish plateau

Continuous methane, CH₄, concentrations were measured in a rural area of the upper Spanish plateau from June 2010 to May 2012 by cavity ring-down spectroscopy technique. The results obtained have proven the local impact of anthropogenic nearby sources on CH₄ concentrations, and evidence a significant influence on the overall mean, averaged daily and seasonal patterns recorded at the measuring site. The positive anomalies in CH₄ concentrations, statistically significant at 95 %, in the southeast sector, defined here as ESE, SE, SSE and S sectors, have been attributed to the contribution of the Valladolid urban plume and the urban landfill. Based on this finding, CH₄ background levels were associated to the concentrations recorded in the remaining un-disturbed sectors. CH₄ means of the overall data set, the southeast sector and background sectors yielded average means of 1,894.1, 1,927.9 and 1,887.1 ppb, respectively. The diurnal and seasonal patterns of the overall data set and background concentrations have shown that CH₄ concentrations are mainly dominated by its reaction with OH radicals. Maximum hourly concentrations were reached during night-time and early morning, 5–7 h, whereas minimum concentrations were recorded at 16 h. Maximum and minimum monthly means were recorded in January and July, respectively. The diurnal and seasonal amplitudes, namely, peak-to-peak means, of background concentrations were 25.1 and 48.1 ppb, respectively. These values were significantly lower than those obtained for the overall data set, 42.9 and 58.1 ppb, revealing the significant role of local influences on CH₄ concentrations despite the low frequency of southeast winds recorded at the measuring site, 16.9 %.