In situ chemical oxidation: Lessons learned at multiple sites

This paper compiles a detailed set of in situ chemical oxidation (ISCO) lessons learned pertaining to design, execution, and safety based on global experiences over the last 20 years. While the benefits of a “correct” application are known (e.g., cost effectiveness, speed, permanence of treatment), history also provides examples of a variety of “incorrect” applications. These provide an opportunity to highlight recurring themes that resulted in failures. ISCO is, and will continue to provide, an important remedial tool for site remediation, particularly as a component of a multifaceted approach for addressing large and complex sites. Future success, however, requires an objective understanding of both the benefits and the limitations of the technology. The ability to learn from the mistakes of the past provides an opportunity to eliminate, or at least minimize, them in the future. Over the last 25 years of ISCO application, process understanding and knowledge have improved and evolved. This paper combines a thorough discussion of lessons learned through decades of ISCO implementation throughout all aspects of ISCO projects with an analysis of changes to the ISCO remediation market. By discussing the interplay of these two themes and providing recommendations from collective lessons learned, we hope to improve the future of safe, cost‐effective, and successful applications of ISCO.     

Heavy metal contamination in sediments of an artificial reservoir impacted by long-term mining activity in the Almadén mercury district (Spain)

Sediments from the Castilseras reservoir, located downstream on the Valdeazogues River in the Almadén mercury district, were collected to assess the potential contamination status related to metals(oids) associated with river sediment inputs from several decommissioned mines. Metals(oids) concentrations in the reservoir sediments were investigated using different physical and chemical techniques. The results were analyzed by principal component analysis (PCA) to explain the correlations between the sets of variables. The degree of contamination was evaluated using the enrichment factor (EF) and the geoaccumulation index (Igeo). PCA revealed that the silty fraction is the main metals(oids) carrier in the sediments. Among the potentially harmful elements, there is a group (Al, Cr, Cu, Fe, Mn, Ni, and Zn) that cannot be strictly correlated to the mining activity since their concentrations depend on the lithological and edaphological characteristics of the materials. In contrast, As, Co, Hg, Pb, and S showed significant enrichment and contamination, thus suggesting relevant contributions from the decommissioned mines through fluvial sediment inputs. As far as Hg and S are concerned, the high enrichment levels pose a question concerning the potential environmental risk of transfer of the organic forms of Hg (mainly methylmercury) from the bottom sediments to the aquatic food chain.     

Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.     

Lessons from Integrating Fishers of Arapaima in Small-Scale Fisheries Management at the Mamirauá Reserve,Amazon

Fishers and small-scale fisheries worldwide have been marginalized historically. Now it is clear that integrating fishers in management processes is key to resource conservation, but it is less clear how to do it. Here, based on a literature review and new information, we present and analyze a case in which the participation of fishers in the management process was crucial in recovering an overexploited small-scale fishery for the pirarucu (Arapaima spp.) in the Amazon Basin, Brazil. In 8 years of experimental management, from 1999 to 2006, the population of pirarucu increased 9-fold (from about 2200 to 20,650 individuals), harvest quotas increased 10-fold (from 120 to 1249 individuals), and fishers’ participation in the management process increased and they benefited from increased monetary returns. Additionally, the number of communities conducting the management scheme increased from 4 in 1999 to 108 in 2006, following the demands of fishers and regional government agencies. Based on our analysis, we suggest that the participation of fishers in the management of other small-scale fisheries in the world can be improved by focusing on (1) applying the knowledge and skills of fishers in resource monitoring and management, (2) bridging knowledge systems among all involved stakeholders, (3) collaborating with fishers that are interested in, and capable of conducting, resource conservation schemes, and (4) conducting management under conditions of uncertainty.     

Long-Term Changes in Game Species Over a Long Period of Transformation in the Iberian Mediterranean Landscape

Agricultural change has transformed large areas of traditional farming landscapes, leading to important changes in the species community assemblages in most European countries. We suspect that the drastic changes in land-use that have occurred in Andalusia (southern Spain) over recent decades, may have affected the distribution and abundance of game species in this region. This article compares the distribution of the main game species in Andalusia during the 1960s and 1990s, using data from maps available from the Mainland Spanish Fish, Game and National Parks Service and from recent datasets on hunting yield distributions, respectively. Big-game and small-game species were significantly segregated in southern Spain during the 1990s, as two clearly independent chorotypes (groups of species whose abundances are similarly distributed) were obtained from the classification analysis. In contrast, big-game and small-game species were not significantly segregated several decades ago, when there was only one chorotype consisting of small-game species and wild boar. The other three ungulates did not constitute a significant chorotype, as they showed positive correlations with some species in the group mentioned above. These changes seem to be a consequence of the transformations that have occurred in the Iberian Mediterranean landscape over the last few decades. The abandoning of traditional activities, and the consequent formation of dense scrubland and woodland, has led to an expansion of big-game species, and a decrease of small-game species in mountain areas. Moreover, agricultural intensification has apparently depleted small-game species populations in some agricultural areas. On the other hand, the increasingly intensive hunting management could be artificially boosting this segregation between small-game and big-game species. Our results suggest that the conservation and regeneration of traditional agricultural landscapes (like those predominating in the 1960s) should be a priority for the conservation of small-game species.     

Use of Descriptors of Ecosystem Functioning for Monitoring a National Park Network: A Remote Sensing Approach

Baseline assessments and monitoring of protected areas are essential for making management decisions, evaluating the effectiveness of management practices, and tracking the effects of global changes. For these purposes, the analysis of functional attributes of ecosystems (i.e., different aspects of the exchange of matter and energy) has advantages over the traditional use of structural attributes, like a quicker response to disturbances and the fact that they are easily monitored through remote sensing. In this study, we described the spatiotemporal patterns of different aspects of the ecosystem functioning of the Spanish national parks and their response to environmental changes between 1982 and 2006. To do so, we used the NOAA/AVHRR-GIMMS dataset of the Normalized Difference Vegetation Index (NDVI), a linear estimator of the fraction of photosynthetic active radiation intercepted by vegetation, which is the main control of carbon gains. Nearly all parks have significantly changed during the last 25 years: The radiation interception has increased, the contrast between the growing and nongrowing seasons has diminished, and the dates of maximum and minimum interception have advanced. Some parks concentrated more changes than others and the degree of change varied depending on their different environmental conditions, management, and conservation histories. Our approach identified reference conditions and temporal changes for different aspects of ecosystem functioning, which can be used for management purposes of protected areas in response to global changes.     

Age and lost working days as a result of an occupational accident: A study in a shiftwork rotation system

The present work analyzed the relationship of age and tenure with occupational accident severity of 156 male shiftworkers at an industrial plant. Based on past research, negative binomial regression analyses were performed to examine the association of age and tenure with the lost working days due to medically certified occupational accidents (LWDI). The main effects of age and tenure and the contribution of age by tenure interaction and age squared terms were examined. Regression results indicated a significant association of age by tenure interaction with LWDI. However, this relationship was non-significant when considering an age squared term in the regression equation, suggesting a non-linear association of age with LWDI. The findings are discussed in regard to the specific preventative measures of occupational accidents in shiftwork systems that could be addressed to different age groups.     

Investigative monitoring within the European Water Framework Directive: a coastal blast furnace slag disposal, as an example

The European Water Framework Directive (WFD) establishes a framework for the protection of estuarine and coastal waters, with the most important objective being to achieve 'good ecological status' for all waters, by 2015. Hence, Member States are establishing programmes for the monitoring of water quality status, through the assessment of ecological and chemical elements. These monitoring programmes can be of three types: surveillance monitoring; operational monitoring (both undertaken on a routine basis); and investigative monitoring (carried out where the reason of any exceedance for ecological and chemical status is unknown). Until now, nothing has been developed in relation to investigative monitoring and no clear guidance exists for this type of monitoring, as it must be tackled on a 'case-by-case' basis. Consequently, the present study uses slag disposal from a blast furnace, into a coastal area, as a case-study in the implementation of investigative monitoring, according to the WFD.In order to investigate the potential threat of such slags, this contribution includes: a geophysical study, to determine the extent of the disposal area; sediment analysis; a chemical metal analysis; and an ecotoxicological study (including a Microtox test and an amphipod bioassay). The results show that metal concentrations are several times above the background concentration. However, only one of the stations showed toxicity after acute toxicological tests, with the benthic communities being in a good status. The approaches used here show that contaminants are not bioavailable and that no management actions are required with the slags.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.