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.     

Influence of temperature on the chemical removal of 3-methylbutanal,trans-2-methyl-2-butenal,and 3-methyl-2-butenal by OH radicals in the troposphere

Absolute rate coefficients for the gas-phase reactions of OH radical with 3-methylbutanal (k₁), trans-2-methyl-2-butenal (k₂), and 3-methyl-2-butenal (k₃) have been obtained with the pulsed laser photolysis/laser-induced fluorescence technique. Gas-phase concentration of aldehydes was measured by UV absorption spectroscopy at 185 nm. Experiments were performed over the temperature range of 263–353 K at total pressures of helium between 46.2 and 100 Torr. No pressure dependence of all k_i (i = 1–3) was observed at all temperatures. In contrast, a negative temperature dependence of k_i (i.e., k_i increases when temperature decreases) was observed in that T range. The resulting Arrhenius expressions (±2σ) are: k₁(T) = (5.8 ± 1.7)×10^?12 exp{(499 ± 94)/T} cm³ molecule^?1 s^?1, k₂(T)=(6.9 ± 0.9)×10^?12 exp{(526 ± 42)/T} cm³ molecule^?1 s^?1, k₃(T)=(5.6 ± 1.2)×10^?12 exp{(666 ± 54)/T} cm³ molecule^?1 s^?1.The tropospheric lifetimes derived from the above OH-reactivity trend are estimated to be higher for 3-methylbutanal than those for the unsaturated aldehydes. A comparison of the tropospheric removal of these aldehydes by OH radicals with other homogeneous degradation routes leads to the conclusion that this reaction can be the main homogeneous removal pathway. However, photolysis of these aldehydes in the actinic region (λ > 290 nm) could play an important role along the troposphere, particularly for 3-methyl-2-butenal. This process could compete with the OH reaction for 3-methylbutanal or be negligible for trans-2-methyl-2-butenal in the troposphere.     

Effect of initial sulfide concentration on sulfide and phenol oxidation under denitrifying conditions

The objective of this work was to evaluate the effect of the initial sulfide concentration on the kinetics and metabolism of phenol and sulfide in batch bioassays using nitrate as electron acceptor. Complete oxidation of sulfide (20 mg L(-1) of S(2-)) and phenol (19.6 mg L(-1)) was linked to nitrate reduction when nitrate was supplemented at stoichiometric concentrations. At 32 mg L(-1) of sulfide, oxidation of sulfide and phenol by the organo-lithoautotrophic microbial culture was sequential; first sulfide was rapidly oxidized to elemental sulfur and afterwards to sulfate; phenol oxidation started once sulfate production reached a maximum. When the initial sulfide concentration was increased from 20 to 26 and finally to 32 mg L(-1), sulfide oxidation was inhibited. In contrast phenol consumption by the denitrifying culture was not affected. These results indicated that sulfide affected strongly the sulfide oxidation rate and nitrate reduction.     

The role of physical processes controlling the behaviour of radionuclide contaminants in the aquatic environment: a review of state-of-the-art modelling approaches

This paper is aimed at presenting and discussing the methodologies implemented in state-of-the-art models for predicting the physical processes of radionuclide migration through the aquatic environment, including transport due to water currents, diffusion, settling and re-suspension. Models are briefly described, model parameter values reviewed and values recommended. The different modelling approaches are briefly classified and the advantages and disadvantages of the various model approaches and methodologies are assessed.     

Interspecies and spatial trends in polycyclic aromatic hydrocarbons (PAHs) in Atlantic and Mediterranean pelagic seabirds

PAHs were analyzed in the liver of 5 species of pelagic seabirds (Procellariiformes) from the northeast Atlantic and the Mediterranean. The main objective was to assess the trophic and geographic trends of PAHs in seabirds to evaluate their suitability as bioindicators of chronic marine pollution by these compounds. Although higher levels of PAHs have been described in the Mediterranean compared to other oceanic regions, we did not find significant spatial patterns and observed only minor effects of the geographic origin on seabird PAHs. However, we found significant higher PAH levels in petrel compared to shearwater species, which could be related to differences in their exploitation of mesopelagic and epipelagic resources, respectively, and the vertical dynamic of PAHs in the water column. Overall, although this study enhances the need of multi-species approaches to show a more comprehensive evaluation of marine pollution, seabirds emerged as poor indicators of pelagic chronic PAH levels.     

New DDT inputs after 30 years of prohibition in Spain. A case study in agricultural soils from south-western Spain

This study provides information on the current status of contamination by DDT in agricultural soils in south-western Spain. A recent use of technical DDT in at least 17% of the soils was found based on the values (<1) of the ratio Rp,p^′/p,p^′=[p,p^′-DDE+p,p^′-DDD]/[p,p^′-DDT]. According to the ratio Ro,p^′/p,p^′=[o,p^′-DDT]/[p,p^′-DDT], a dicofol type contamination was detected in about 27% of the soils. A wide range of concentrations was observed (0.08-11.1 ng/g d.w.) regardless of the type of crop soil. Enantiomeric fractions (EFs), based on the chiral analysis of o,p′-DDT residues differed from the racemic value (0.500) in most soils but they were not correlated with the study variables [DDTs], SOM, Rp,p^′/p,p^′ and Ro,p^′/p,p^′. Given the health risks posed by DDT, our findings support how the environmental control of legacy pollutants such as DDT cannot be neglected.     

Stoichiometric and molecular evidence for the enrichment of anaerobic ammonium oxidizing bacteria from wastewater treatment plant sludge samples

Anammox enrichments were readily developed from seven municipal wastewater treatment plants (WWTPs) sludge, but not with methanogenic granular sludge from two agro-industrial WWTPs. Only 50 d was required for the first evidence of anammox activity from a return activated sludge obtained from a WWTP operated for nutrient removal. The molar ratios of nitrite and ammonium consumption of approximately 1.32 as well as nitrate and dinitrogen gas product ratios of approximately 0.095 provided evidence of the anammox reaction. The presence of anammox was confirmed by polymerase chain reaction (PCR) using primer sets (PLA46F and AMX820R) specific for anammox bacteria. The 16S rRNA gene fragment of anammox bacteria was detected in seven enrichment cultures (ECs) with demonstrated anammox activity but not in the original inocula from which the ECs were derived and also not in the two methanogenic sludge samples, which indicates the PCR predicted the anammox activity. Two genera, Brocadia and Kuenenia, were successfully identified as the Planctomycetes occurring in the clone libraries of successful anammox enrichments. Brocadia dominated in cultures that were respiked extensively; whereas Kuenenia predominated in cultures that were less aggressively respiked. These findings indicate that respiking management may play an important role on selecting the genus of anammox bacteria. The batch enrichment results clearly illustrate that anammox can be readily enriched from municipal sludge from a wide variety of process operations at WWTPs.     

Biofiltration kinetics of a gaseous aldehyde mixture using a synthetic matrix

Although aldehydes contribute to ozone and particulate matter formation, there has been little research on the biofiltration of these volatile organic compounds (VOCs), especially as mixtures. Biofiltration degradation kinetics of an aldehyde mixture containing hexanal, 2-methylbutanal (2-MB), and 3-methylbutanal (3-MB) was investigated using a bench-scale, synthetic, media-based biofilter. The adsorption capacity of the synthetic media for a model VOC, 3-methylbutanal, was 10 times that of compost. Periodic residence time distribution analysis (over the course of 1 yr) via a tracer study (84-99% recovery), indicated plug flow without channeling in the synthetic media and lack of compaction in the reactor. Simple first-order and zero-order kinetic models both equally fit the experimental data, yet analysis of the measured rate constants versus fractional conversion suggested an overall first-order model was more appropriate. Kinetic analysis indicated that hexanal had a significantly higher reaction rate (k = 0.09 +/- 0.005 1/sec; 23 +/- 1.3 ppmv) compared with the branched aldehydes (k = 0.04 +/- 0.0036 1/sec; 31 +/- 1.6 ppmv for 2-MB and 0.03 +/- 0.0051 1/sec; 22 +/- 1.3 ppmv for 3-MB). After 3 months of operation, all three compounds reached 100% removal (50 sec residence time, 18-46 ppmv inlet). Media samples withdrawn from the biofilter and observed under scanning electron microscopy analysis indicated microbial growth, suggesting removal of the aldehydes could be attributed to biodegradation.     

Ozone Predictions in Atlanta,Georgia: Analysis of the 1999 Ozone Season

ABSTRACT

Ozone prediction has become an important activity in many U.S. ozone nonattainment areas. In this study, we describe the ozone prediction program in the Atlanta metropolitan area and analyze the performance of this program during the 1999 ozone-forecasting season. From May to September, a team of 10 air quality regulators, meteorologists, and atmospheric scientists made a daily prediction of the next-day maximum 8-hr average ozone concentration. The daily forecast was made aided by two linear regression models, a 3-dimensional air quality model, and the no-skill ozone persistence model. The team's performance is compared with the numerical models using several numerical indicators. Our analysis indicated that (1) the team correctly predicted next-day peak ozone concentrations 84% of the time, (2) the two linear regression models had a better performance than a 3-dimensional air quality model, (3) persistence was a strong predictor of ozone concentrations with a performance of 78%, and (4) about half of the team's wrong predictions could be prevented with improved meteorological predictions.     

Mortality of the scleractinian coral <Emphasis Type="Italic">Cladocora caespitosa</Emphasis> during a warming event in the Levantine Sea (Cyprus)

A mortality event of Cladocora caespitosa corals and the extent of bleaching, necrosis and pigmented areas in the colonies were studied at the southeastern coast of Cyprus during a prolonged period of higher than average sea temperature anomalies (summer/autumn 2012). With the use of scuba diving and image analysis software, we monitored the extent of mortality of 29 colonies of C. caespitosa by measuring and comparing the area percentage of healthy tissue, affected tissue (bleached, necrotic) and older mortality events (encrusted skeleton). In September 2012, on average, 24 % of the colonies surface area was affected (bleaching and/or necrosis). In October 2012, C. caespitosa showed on average 26.3 % of the colony surface area affected, evidence of continuing deterioration. At the same time, 10 % (3 of 29) of the colonies showed an increase in the pigmentation of previously bleached polyps in small and marginal areas (6–8 %). Irrespective of the amount, the regaining of pigments recorded is considered an important find. Corals and marine organisms in general in the Levantine Sea are affected greatly by warming events, to the extent where a very small percentage of polyps/colonies show resilience under thermal stress. Natural bleaching of C. caespitosa, even though limited to a few colonies and very small portions of tissue/polyps, was documented for the first time in the Levantine Sea. We conclude that temperature anomalies are associated with the mortality event. Whether prolonged higher temperature is the direct cause, or whether it acts synergistically with other factors should be the subject of further investigations.