Kinetics of the sensitized photodegradation of nonylphenol

Nonylphenol (nonyl‐P) belongs to the classification of persistent organic pollutants. In this work we demonstrate that the contaminant suffers photooxygenation when exposed to visible light Eosin‐photosensitized irradiation. The mechanism was identified as a singlet molecular oxygen‐mediated photooxidation. Rate constants for the process, determined by time‐resolved phosphorescence detection of singlet molecular oxygen, are in the range 10⁵‐10⁷ M^‐1 s^‐1, depending on the characteristics of the reaction medium. The photooxidative process is more efficient when performed in highly polar alkaline medium.

The aggregation of nonyl‐P molecules in pure water decreases the rates of sensitized photooxidation of nonyl‐P and also those of polychlorophenolic contaminants, employed as photooxidizable model compounds, when photolyzed in the presence of nonylphenol. These results are discussed in terms of a micellar effect.     

Wave hydrodynamics around a multi-functional artificial reef at Leirosa

This paper describes an application of the Boussinesq-type COULWAVE model to study the wave hydrodynamics in the vicinity of a multi-functional artificial reef (MFAR). This reef is under investigation and consists of a supplementary protection solution for the Leirosa sand dune system located at South of Figueira da Foz, on the Portuguese West coast. Such installation near the coastline is expected to contribute to enhance the surfing conditions in the area, protect the sand dune system in the surroundings of Leirosa beach, and increase its environmental value. Numerical calculations with the COULWAVE model were performed for four test cases, considering two reef geometries (differing in the reef angle) and two incident wave conditions (storm condition and a common wave condition). Comparisons between the results obtained, in terms of wave heights and breaking line positions allow us to assess the influence of the reef on the hydrodynamics near the beach and around the reef. Moreover, the reef performance was analysed in terms of surfability and coastal protection. The surfability parameters (breaker height, Iribarren number and peel angle) were calculated for each test case using the numerical wave heights, wave directions and wave breaking positions. Comparisons of parameters allow characterizing the most appropriate configuration of the reef to improve the surfing conditions in the study area. A methodology based on numerical free surface elevations and horizontal velocity components was developed to calculate wave directions, since this is not a direct output of the COULWAVE model. Concerning coastal protection, analyses of the mean currents around the reef were used together with observations of the velocity cells near the shoreline as an indication of the sediment transport.     

Design and first experimental results of a bubbling fluidized bed for air gasification of plastic waste

Plastic wastes have an especially high potential for use as alternative fuels, considering their high heating value and their large and stable availability. They could be used in electricity production based on gasification technologies, wherein electricity is produced in engines by means of the conversion of plastic wastes into a valuable gas. However, there are still some technical barriers to overcome before this technology can access the commercial stage, and further scientific research is needed to gain deeper understanding of the process and to be able to control and optimize it. This research presents the design and first experimental results of a bubbling fluidized bed gasifier conceived for the gasification of actual plastic residues. The experimental tests revealed that the selection and design of the reactor were adequate and proved some of the advantages of using plastic as a fuel, related in part to the absence of ashes and char. A valuable syngas over 5 MJ/m³ was generated, which contained a considerable fraction of methane as well as hydrogen and carbon monoxide as main combustible gases. The highest efficiency was achieved when the equivalence ratio was increased to 0.35, reaching 61 % in terms of cold gas efficiency and 66 % carbon conversion.     

Coastal management research: a personal reflection on the conference outcome

Communication between scientific disciplines related to coastal management is difficult but essential. Different views on the role of science in coastal management were key elements of many discussions at the conference. In this personal impression the author looks back and reflects on the arguments which participants with different scientific back-ground exchanged.     

They don't want to be temporaries: similarities between temps and core workers

This study investigated the impact of employment status (temporary/regular) on the employee–organization relationship in samples from two firms employing both temps (n = 234) and regular or core (n = 204) workers. Temps and regular workers held similar beliefs regarding the nature of their employment relationship. However, among those temps for whom temporary work was their preferred status, the employment relationship was less socioemotional and more economic than was the case for other workers. When these temps preferred regular employment, their relationships were high socioemotional and low economic, comparable with that of core workers. A employee–organization relationship high on socioemotional terms was positively related to satisfaction with the organization, an attitude which in turn mediated the relationship between employment relationship and employees' performance and civic virtue behaviors (behaviors as assessed by their supervisors). Copyright © 2007 John Wiley & Sons, Ltd.     

Assessment of Coastal Vulnerability Through the Use of GIS Tools in South Sicily (Italy)

This study assessed coastal erosion vulnerability along a 90-km sector, which included both erosional and accretionary beaches, and different levels of human occupation. Two aerial photogrammetric flights were used to reconstruct coastal evolution between 1977 and 1999. During this period, extensive accretion was recorded updrift of human structures at harbors and ports, e.g., Scoglitti (105.6 m), Donnalucata (52.8 m), and Pozzallo (94.6 m). Conversely, erosion was recorded in downdrift areas, with maximum values at Modica Stream mouth (63.8 m) and Point Castellazzo (35.2 m). Assessments were subsequently divided into four categories ranging from “high erosion” to “accretion.” Several sources were examined to assess human activities and land use. The latter was mapped and divided into four categories, ranging from “very high” to “no capital” land use. Subsequently, coastal erosion vulnerability was assessed by combining land use categories with recorded coastline behavior. Results showed “very high” to “high” vulnerability along 5.8% and 16.6%, respectively, of the littoral, while 20.9% and 56.7%, respectively, was found to exhibit “medium” and “low/very low” vulnerability. A very good agreement between predicted coastal vulnerability and coastal trend had been observed over recent years. Furthermore, several human structures and activities are located within the “imminent collapse zone (ICZ)” which reached maximum values of 17.5 m at Modica Stream and 13.5 m at Point Braccetto.     

The origin of speciation: trace metal kinetics over natural water/sediment interfaces and the consequences for bioaccumulation

The speciation of heavy metals was measured over a variety of natural and undisturbed water/sediment interfaces. Simultaneously, two benthic species (oligochaete Limnodrilus spp. and the midge Chironomus riparius) were exposed to these sediments. Under occurring redox conditions, free ion activities of trace metals Cd, Cu, Ni, Pb, and Zn were measured with a chelating exchange technique, while geochemical conditions (i.e., redox) remained in tact. Free ion activities were compared with total dissolved concentrations in pore waters and surface waters in order to relate speciation to bioaccumulation. Limnodrilus spp. and C. riparius have accumulation patterns that could be linked to time-dependent exposure concentrations, expressed as chemical speciation, in the surface water and the sediment's pore water. Concentrations of free metal ions in the overlying surface water, rather than in sediment pore water, proved to be the best predictor for uptake. For the first time, measurements are obtained from sediments without disturbing physical-chemical conditions and thus bioavailability, a major restriction of other studies so far.     

Cost–benefit analysis of using sewage sludge as alternative fuel in a cement plant: a case study

Background, aim, and scope  To enforce the implementation of the Kyoto Protocol targets, a number of governmental/international institutions have launched emission trade schemes as an approach to specify CO₂ caps and to regulate the emission trade in recent years. These schemes have been basically applied for large industrial sectors, including energy producers and energy-intensive users. Among them, cement plants are included among the big greenhouse gas (GHG) emitters. The use of waste as secondary fuel in clinker kilns is currently an intensive practice worldwide. However, people living in the vicinity of cement plants, where alternative fuels are being used, are frequently concerned about the potential increase in health risks. In the present study, a cost–benefit analysis was applied after substituting classical fuel for sewage sludge as an alternative fuel in a clinker kiln in Catalonia, Spain. Materials and methods  The economical benefits resulting in the reduction of CO₂ emissions were compared with the changes in human health risks due to exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and carcinogenic metals (As, Cd, Co, and Cr) before and after using sewage sludge to generate 20% of the thermal energy needed for pyro-processing. The exposure to PCDD/Fs and metals through air inhalation, soil ingestion and dermal absorption was calculated according to the environmental levels in soil. The carcinogenic risks were assessed, and the associated cost for the population was estimated by considering the DG Environment’s recommended value for preventing a statistical fatality (VPF). In turn, the amount of CO₂ emitted was calculated, and the economical saving, according to the market prices, was evaluated. Results  The use of sewage sludge as a substitute of conventional energy meant a probability cancer decrease of 4.60 for metals and a cancer risk increase of 0.04 for PCDD/Fs. Overall, a net reduction of 4.56 cancers for one million people can be estimated. The associated economical evaluation due to the decreasing cancer for 60,000 people, the current population living near the cement plant, would be of 0.56 million euros (US$ 0.83 million). In turn, a reduction of 144,000 tons of CO₂ emitted between 2003 and 2006 was estimated. Considering a cost of 20 euros per ton of CO₂, the global saving would be 2.88 million euros (US$ 4.26 million). Discussion  After the partial substitution of the fuel, the current environmental exposure to metals and PCDD/Fs would even mean a potential decrease of health risks for the individuals living in the vicinity of the cement plant. The total benefit of using sewage sludge as an alternative fuel was calculated in 3.44 million euros (US$ 5.09 million). Environmental economics is becoming an interesting research field to convert environmental benefits (i.e., reduction of health risks, emission of pollutants, etc.) into economical value. Conclusions  The results show, that while the use of sewage sludge as secondary fuel is beneficial for the reduction in GHG emissions, no additional health risks for the population derived from PCDD/F and metal emissions are estimated. Recommendations and perspectives  Cost–benefit analysis seems to be a suitable tool to estimate the environmental damage and benefit associated to industrial processes. Therefore, this should become a generalized practice, mainly for those more impacting sectors such as power industries. On the other hand, the extension of the study could vastly be enlarged by taking into account other potentially emitted GHGs, such as CH₄ and N₂O, as well as other carcinogenic and non-carcinogenic micropollutants.     

Effects of public health interventions on industrial emissions and ambient air in Cartagena, Spain

Background, aim, and scope

Ten years of public health interventions on industrial emissions to clean air were monitored for the Mediterranean city of Cartagena. During the 1960s, a number of large chemical and non-ferrous metallurgical factories were established that significantly deteriorated the city’s air quality. By the 1970s, the average annual air concentration of sulfur dioxide (SO₂) ranged from 200 to 300 µg/m³ (standard conditions units). In 1979, the Spanish government implemented an industrial intervention plan to improve the performance of factories and industrial air pollution surveillance. Unplanned urban development led to residential housing being located adjacent to three major factories. Factory A produced lead, factory B processed zinc from ore concentrates, and factory C produced sulfuric acid and phosphates. This, in combination with the particular abrupt topography and frequent atmospheric thermal inversions, resulted in the worsening of air quality and heightening concern for public health. In 1990, the City Council authorized the immediate intervention at these factories to reduce or shut down production if ambient levels of SO₂ or total suspended particles (TSP) exceeded a time-emission threshold in pre-established meteorological contexts. The aim of this research was to assess the appropriateness and effectiveness of the intervention plan implemented from 1992 to 2001 to abate industrial air pollution.

Materials and methods

The maximum daily 1-h ambient air level of SO₂, NO₂, and TSP pollutants was selected from one of the three urban automatic stations, designed to monitor ambient air quality around industrial emissions sources. The day on which an intervention took place to reduce and/or interrupt industrial production by factory and pollutant was defined as a control day, and the day after an intervention as a post-control day. To assess the short-term intervention effect on air quality, an ecological time series design was applied, using regression analysis in generalized additive models, focusing on day-to-day variations of ambient air pollutants levels. Two indicators were estimated: (a) appropriateness, the ratio between mean levels of the pollutant for control days versus the other days, and (b) effectiveness, the ratio between mean levels of the pollutant for post-control days versus the other days. Ratios in regression analyses were adjusted for trend, seasonality, temperature, humidity and atmospheric pressure, calendar day, and special events as well as the other pollutants.

Results

A total of 702 control days were made on the factories’ industrial production during the 10-year period. Fifteen reductions and five shutdown control days took place at factory A for ambient air SO₂. At factory B, more controls were carried out for the SO₂ pollutant in the years 1992–1993 and 1997. At factory C, the control days for SO₂ decreased from 59 reductions and 14 shutdowns to a minimum from 1995 onwards, whereas the controls on TSP were more frequent, reaching a maximum of 99 reductions and 47 shutdowns in the last year. SO₂ ambient air mean levels ranged from 456 to 699 µg/m³ among factories on reduction control days and between 624 and 1,010 µg/m³ on shutdown days. The TSP ambient air mean levels were 428 and 506 µg/m³ on reduction and shutdown days, respectively. For all types of control days and factories, a mean ratio of 104% (95% confidence interval [CI] 88 to 121) in SO₂ levels was obtained and a mean ratio of 67% (95% CI 59 to 75) in TSP levels. Post-control days at all factories showed a mean ratio of ?16% (95% CI ?7 to ?24) in SO₂ levels and a mean ratio of ?13% (95% CI ?7 to ?19) in TSP levels.

Discussion

Interventions on industrial production based on the urban SO₂ and TSP ambient air levels were justified by the high concentrations detected. The best assessment of the interventions’ effectiveness would have been to utilize the ambient air pollutant concentration readings from the entire time of the production shutdowns or reductions; however, the daily hourly maximum turned out to be a useful indicator because of meteorological factors influencing the diurnal concentration profile. A substantial number of interventions were carried out from 1 to 3 am, when vehicular traffic was minimum. On the other hand, atmospheric stability undergoes diurnal cycling in the autumn–winter period due to thermal inversion, which reaches maximum levels around daybreak. Therefore, this increases the ambient air levels and justified the interventions carried out at daybreak in spite of the traffic influence.

Conclusions

All the interventions for SO₂ and TSP were carried out when the measured ambient air levels of pollutants were exceeded, which shows the appropriateness of the intervention program. This excess was greater when intervening on SO₂ than on the TSP levels. For both ambient air levels of SO₂ and TSP, significant drops in air pollution were achieved from all three factories following activity reductions. The production shutdown controls were very effective, because they returned excess levels, higher than in the reduction controls, to everyday mean values.

Recommendations and perspectives

The Cartagena City observational system of intermittent control has proven to effectively reduce industrial emissions’ impact on ambient air quality. This experienced model approach could serve well in highly polluted industrial settings. From a public health perspective, studies are needed to assess that the industrial interventions to control air pollution were related to healthier human populations. Legislation was needed to allow the public administration to take direct actions upon the polluting industries.