Performance of a field-scale permeable reactive barrier based on organic substrate and zero-valent iron for in situ remediation of acid mine drainage

A permeable reactive barrier (PRB) was installed in Aznalcóllar (Spain) in order to rehabilitate the Agrio aquifer groundwater severely contaminated with acid mine drainage after a serious mining accident. The filling material of the PRB consisted of a mixture of calcite, vegetal compost and, locally, Fe⁰ and sewage sludge. Among the successes of the PRB are the continuous neutralisation of pH and the removal of metals from groundwater within the PRB (removals of >95 %). Among the shortcomings are the improper PRB design due to the complexity of the internal structure of the Agrio alluvial deposits (which resulted in an inefficient capture of the contaminated plume), the poor degradability of the compost used and the short residence time within the PRB (which hindered a complete sulphate reduction), the clogging of a section of the PRB and the heterogeneities of the filling material (which resulted in preferential flows within the PRB). Undoubtedly, it is only through accumulated experience at field-scale systems that the potentials and limits of the PRB technology can be determined.     

Comparison of Analytical Techniques for Measuring Hydrocarbon Emissions from the Manufacture of Fiberglass-Reinforced Plastics

ABSTRACT

Research Triangle Institute and the U.S. Environmental Protection Agency conducted several projects to measure hydrocarbon emissions associated with the manufacture of fiberglass-reinforced plastics. The purpose of these projects was to evaluate pollution prevention techniques to reduce emissions by altering raw materials, application equipment, and operator technique. Analytical techniques were developed to reduce the cost of these emission measurements. Emissions from a small test mold in a temporary total enclosure (TTE) correlated with emissions from full-size production molds in a separate TTE. Gravimetric mass balance measurements inside the TTE generally agreed to within ± 30 % with total hydrocarbon (THC) measurements in the TTE exhaust duct. Pure styrene evaporation tests served as quality control checks for THC measurements and generally agreed to within ± 5 %.     

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.     

Transcriptional response of stress genes to metal exposure in zebra mussel larvae and adults

Development of stress markers for the invader freshwater zebra mussel (Dreissena polymorpha) is of great interest for both conservation and biomonitoring purposes. Gene expression profiles of several putative or already established gene expression stress markers (Metallothionein, Superoxide dismutase, Catalase, Glutathione S transferase, Glutathione peroxidase, Cytochrome c oxidase, the multixenobiotic resistance P-gp1, and heat shock proteins HSP70 and HSP90) were analyzed by quantitative Real-Time PCR in adults and pediveliger larvae after exposure to metals (Hg, Cu, Cd). A defined pattern of coordinated responses to metal exposure and, presumably, to oxidative stress was observed in gills and digestive gland from adults. A similar, albeit partial response was observed in larvae, indicating an early development of stress-related gene responses in zebra mussel. The tools developed in this study may be useful both for future control strategies and for the use of zebra mussel as sentinel species in water courses with stable populations.     

A chemometric approach to the evaluation of atmospheric and fluvial pollutant inputs in aquatic systems: the Guadalquivir River estuary as a case study

To establish the quality of waters it is necessary to identify both point and non-point pollution sources. In this work, we propose the combination of clean analytical methodologies and chemometric tools to study discrete and diffuse pollution caused in a river by tributaries and precipitations, respectively.During a two-year period, water samples were taken in the Guadalquivir river (selected as a case study) and its main tributaries before and after precipitations. Samples were characterized by analysing nutrients, pH, dissolved oxygen, total and volatile suspended solids, carbon species, and heavy metals. Results were used to estimate fluvial and atmospheric inputs and as tracers for anthropic activities.Multivariate analysis was used to estimate the background pollution, and to identify pollution inputs. Principal Component Analysis and Cluster Analysis were used as data exploratory tools, while box-whiskers plots and Linear Discriminant Analysis were used to analyse and distinguish the different types of water samples.     

Hidden demographic impacts of fishing and environmental drivers of fecundity in a sea turtle population

Fisheries bycatch is a critical threat to sea turtle populations worldwide, particularly because turtles are vulnerable to multiple gear types. The Canary Current is an intensely fished region, yet there has been no demographic assessment integrating bycatch and population management information of the globally significant Cabo Verde loggerhead turtle (Caretta caretta) population. Using Boa Vista island (Eastern Cabo Verde) subpopulation data from capture–recapture and nest monitoring (2013–2019), we evaluated population viability and estimated regional bycatch rates (2016–2020) in longline, trawl, purse-seine, and artisanal fisheries. We further evaluated current nesting trends in the context of bycatch estimates, existing hatchery conservation measures, and environmental (net primary productivity) variability in turtle foraging grounds. We projected that current bycatch mortality rates would lead to the near extinction of the Boa Vista subpopulation. Bycatch reduction in longline fisheries and all fisheries combined would increase finite population growth rate by 1.76% and 1.95%, respectively. Hatchery conservation increased hatchling production and reduced extinction risk, but alone it could not achieve population growth. Short-term increases in nest counts (2013–2021), putatively driven by temporary increases in net primary productivity, may be masking ongoing long-term population declines. When fecundity was linked to net primary productivity, our hindcast models simultaneously predicted these opposing long-term and short-term trends. Consequently, our results showed conservation management must diversify from land-based management. The masking effect we found has broad-reaching implications for monitoring sea turtle populations worldwide, demonstrating the importance of directly estimating adult survival and that nest counts might inadequately reflect underlying population trends.     

Phenol degradation using combined effects of hydrodynamic cavitation and oxidant: Doehlert matrix

Hydrodynamic cavitation (HC)-based treatments have been proposed for the degradation of phenol as a toxic pollutant. The present work aimed to optimize the degradation of phenol using HC by means of Doehlert experimental design, which has not been previously addressed. Initially, operational parameters of hydraulic characteristics of the pump, inlet pressure, solution pH, and initial concentration were optimized; later, the effects of pH solution and H₂O₂ loading or initial pollutant concentration on phenol degradation were explored using the Doehlert experimental design. It was observed that phenol degradation is strongly dependent on the pH of the solution. Also, the acidic condition favors the formation of hydroxyl radicals and thus, the degradation of phenol. Based on the Doehlert matrix, the 94.1% phenol degradation and 68.60% total organic carbon (TOC) were obtained in 180 min at 304.5 mg/L of hydrogen peroxide at an initial concentration of 20 mg/L, 2.0 pH, and 90 psi inlet pressure, providing a cavitational yield of 6.33 × 10⁻⁶ mg/J and minimum treatment cost of US$/L 0.13. Overall, it has been observed that HC can be a promising route for the removal of pollutants (phenol) effectively using hydrogen peroxide as an additive.     

Environmental accounting as a management tool in the Mediterranean context: the Spanish economy during the last 20 years

Although human presence is one of the main characteristics of the Mediterranean identity since ancient times, a false dialectic between conservation and social-economic development has emerged in recent decades. On the one hand, an economic growth policy is taken as the paradigm of social-economic development; on the other hand, there is a multi-scale conservation policy, in which natural protected areas, as patches of preserved nature, are used as one of the main tools to deal with the challenge of sustainability. The Mediterranean Basin is the habitat of many unique species and one of the 25 main biodiversity hotspots in the world, and as a consequence a strong conservation policy has been used to protect environmental values. At the same time, Mediterranean countries are deeply involved in promoting strong economic growth policies, which are not always compatible with environmental ones. In this paper, Spain has been studied as one model of this situation. Due to political reasons, Spanish economic growth and conservationist policies were pursued together during the last 20 years. As a result, Spain owns one of the largest networks of natural protected areas in Western Europe, and at the same time it has experienced one of the strongest periods of economic growths in the European and Mediterranean context during the 1980s and 1990s. An historical series of resource use in five annual periods in the last 20 years of conservation policy, and the effects on the preservation of natural capital have been investigated by means of the eMergy (spelled with an 'm') synthesis approach, which was used to characterize the flow of environmental services supplied by ecosystems, but not in monetary terms. This study shows that Spain is becoming less self-sufficient and more inefficient in resource use, comprehensively measured in eMergy terms. A large part of Spain's economy depends on imported goods and services, and most economic activities are based on tourist services and associated construction, which promotes intensification in the urban use of the territory and more intense environmental impacts and resource use intensification of those countries supplying the raw materials. The consequence is a decoupling of the Spanish economy from local environmental services and the increase of Ecological footprint of Spain, measured by means of eMergy-based indicators. In spite of the increase in number, area and associated budget of the natural protected areas and other conservation measures, the general sustainability of the nation is decreasing.     

First evidence of polybrominated diphenyl ether (flame retardants) effects in feral barbel from the Ebro River basin (NE, Spain)

Polybrominated diphenyl ethers (PBDEs) are chemicals of environmental concern due to their lipophilic, persistent and bioaccumulable characteristics as well as for their potential endocrine disrupting role. Former studies carried out in a tributary of the Cinca river (Ebro basin, NE Spain) revealed high levels of PBDEs in fish due to the discharges of effluents rich in PBDEs coming from a nearby industrial park in Barbastro. In this study, several biomarkers of pollutants exposure were measured in barbel, Barbus graellsii, before (upstream) and after (downstream) the main industrial site (Barbastro) in the Vero river. The results evidenced an enhanced hepatic phase I and II metabolism (measured as reductases, glutathione S transferase and uridinediphospho-glucuronosyltransferase), and of the antioxidant enzyme glutathione peroxidase. Conversely, fishes collected from downstream reaches had their phase I CYP1A dependent ethoxyresorufin O-deethylase, antioxidant diaphorase and brain cholinesterase activities depleted. In addition, the histological study of the liver and kidney of these fish evidenced an increase of the number and size of macrophage aggregates in most individuals collected downstream. Bivariate correlated analyses showed that the above mentioned biomarkers were correlated to measured PBDE congeners, thus indicating that the observed biological effects were unlikely to be related to other environmental factors than PBDEs. Overall, the measured biochemical and histological markers provide new evidence that in field exposed fish, PBDEs levels were associated with high activities of phase I and II metabolic enzymes, oxidative stress in liver, neurotoxicity in brain and histopathological effects in both liver and kidney.     

Contamination Levels and Preliminary Assessment of the Technical Feasibility of Employing Natural Attenuation in 5 Priority Areas of Presidente Bernardes Refinery in Cubatão, São Paulo, Brazil

Five priority areas of potential impact by contaminants (API) were investigated at the Presidente Bernardes Refinery in Cubatão, São Paulo, Brazil with the following aims: (i) to identify both organic and inorganic contaminants present in soil and groundwater; (ii) to define the environmental conditions relevant for microbial activity at the site and (iii) to evaluate the feasibility of employing natural attenuation for treatment of the hydrocarbon contamination. One area (API 1) was an uncontrolled landfill, where waste materials from the refinery were deposited between 1954 and 1986, and four areas (API 4, 5, 7 and 11) were located in the operational section of the refinery. Soil contamination by regulated BTEX compounds (benzene, toluene, total xylenes) was restricted to two samples from API 1. Nonregulated ethylbenzene was detected in one soil sample from API 4, one from API 5 and two from API 1. No soil contained regulated PAH above threshold levels. Several nonregulated PAHs were found in 6 soil samples from API 1, 3 soil samples from API 4 and 1 soil sample from API 5. Site soils contained very high aluminium concentrations, but metal contamination was restricted to one soil sample from API 1, which contained nickel above threshold limits. BTEX contamination of groundwater was due mostly to benzene. Of the 17 PAH molecules tested, only naphthalene and 2-methylnaphthalene occurred in groundwater. The sum of total BTEX and total PAH exceeded 200 μg/L in only a few monitoring wells in API 4, 5 and 11 and was always below 2.640 μg/L. Be, Cd, Cr, Cu, Hg, Ni, Se, Ag, Tl and Zn were not detected in groundwater, which was contaminated in a few locations by aluminium (mostly below 1 mg/L), lead (<0.066 mg/L) and arsenic (<0.056 mg/L). S, K, Ca, Mg and Fe were present in groundwater in excess of physiological requirements for microbial growth, but low concentrations of N and P could become growth limiting. However, BTEX were efficiently degraded in saturated and unsaturated zone microcosms and nutrient amendments did not stimulate biodegradation rates measurably. The inorganic carbon pool in groundwater was up to one order of magnitude larger than the organic carbon pool. Total inorganic carbon (TIC) in API groundwater exceeded TIC of clean groundwater by factors of 2 (API 4), 6 (API 5, 7 and 11) or 10 (API 1). Most of the inorganic carbon incorporated into groundwater beneath the refinery originated from biodegradation in the unsaturated soil, which contained a microbiota (10⁶ cells/g on average) capable of growth with most of the pure (benzene, toluene, ethylbenzene and xylene) and mixed hydrocarbons tested (diesel oil, gasoline, naphtha, condensate, aromatic residue and fuel oil). A viscous hydrocarbon paste uncovered in API 1 was insoluble in water but dissolved in dichloromethane. Many organic components of this paste were biodegradable as evidenced by weight reduction of the hydrocarbon paste and by the growth of suspended and attached biomass in saturated zone microcosms, where the paste was the only carbon source. This study indicates that monitored natural attenuation may be a technically feasible and efficient means for plume control in API 1, 4 and 5, provided the plumes in API 4 and 5 are not expanding. This technique is not suitable for contaminant reduction in API 11.