Nonparametric functional data estimation applied to ozone data: prediction and extreme value analysis

The study of extreme values and prediction of ozone data is an important topic of research when dealing with environmental problems. Classical extreme value theory is usually used in air-pollution studies. It consists in fitting a parametric generalised extreme value (GEV) distribution to a data set of extreme values, and using the estimated distribution to compute return levels and other quantities of interest. Here, we propose to estimate these values using nonparametric functional data methods. Functional data analysis is a relatively new statistical methodology that generally deals with data consisting of curves or multi-dimensional variables. In this paper, we use this technique, jointly with nonparametric curve estimation, to provide alternatives to the usual parametric statistical tools. The nonparametric estimators are applied to real samples of maximum ozone values obtained from several monitoring stations belonging to the Automatic Urban and Rural Network (AURN) in the UK. The results show that nonparametric estimators work satisfactorily, outperforming the behaviour of classical parametric estimators. Functional data analysis is also used to predict stratospheric ozone concentrations. We show an application, using the data set of mean monthly ozone concentrations in Arosa, Switzerland, and the results are compared with those obtained by classical time series (ARIMA) analysis.     

Agricultural adjustment,population dynamics and forests redistribution in a subtropical watershed of NW Argentina

Patterns of land-use and land-cover change are usually grouped into one of two categories defined by the dominant trend: (1) deforestation resulting from expanding agriculture and (2) forest expansion, usually related to the abandonment of marginal lands. At regional scale, however, both processes can occur simultaneously even in the absence of net change. Given the focus on net change, such redistribution of agricultural and natural and seminatural lands has been generally overlooked. The interaction between agriculture modernization, human demography and complex topographic gradients of northwestern Argentina has resulted in processes of both forest recovery and deforestation, thus providing the opportunity to analyze patterns and driving forces of land-cover redistribution. We analyzed 20 years (1986–2006) of land-cover change in a subtropical watershed in relation to topographic and demographic variables. Although net forest change represented <1 %, forests redistribution affected 7 % of forest lands. There was a consistent geographic segregation of deforestation and forest recovery, with forests expanding over steep highlands and agriculture expanding over lowland irrigated areas. Population trends were not associated to forest expansion in lowlands but they explained 32 % of forest recovery in highlands. Highland forest expansion and lowland deforestation, respectively, imply conservation opportunities for humid montane forests and the environmental services they provide (e.g., watershed conservation) and threats for the conservation of dry forests and its biodiversity. Our study exemplifies the importance of land-use redistribution (rather than net change) with relevant environmental consequences at regional scale.     

Building resilience to water scarcity in southern Spain: a case study of rice farming in Doñana protected wetlands

Agricultural water management needs to evolve in view of increased water scarcity, especially when farming and natural protected areas are closely linked. In the study site of Doñana (southern Spain), water is shared by rice producers and a world heritage biodiversity ecosystem. Our aim is to contribute to defining adaptation strategies that may build resilience to increasing water scarcity and minimize water conflicts among agricultural and natural systems. The analytical framework links a participatory process with quantitative methods to prioritize the adaptation options. Bottom-up proposed adaptation measures are evaluated by a multi-criteria analysis (MCA) that includes both socioeconomic criteria and criteria of the ecosystem services affected by the adaptation options. Criteria weights are estimated by three different methods—analytic hierarchy process, Likert scale and equal weights—that are then compared. Finally, scores from an MCA are input into an optimization model used to determine the optimal land-use distribution in order to maximize utility and land-use diversification according to different scenarios of funds and water availability. While our results show a spectrum of perceptions of priorities among stakeholders, there is one overriding theme that is to define a way to restore part of the rice fields to natural wetlands. These results hold true under the current climate scenario and even more so under an increased water scarcity scenario.     

Phosphorus and sulfur in a tropical soil and their effects on growth and selenium accumulation in Leucaena leucocephala (Lam.) de Wit

Selenium (Se) is an essential metalloid element for mammals. Nonetheless, both deficiency and excess of Se in the environment are associated with several diseases in animals and humans. Here, we investigated the interaction of Se, supplied as selenate (Se⁺⁶) and selenite (Se⁺⁴), with phosphorus (P) and sulfur (S) in a weathered tropical soil and their effects on growth and Se accumulation in Leucaena leucocephala (Lam.) de Wit. The P-Se interaction effects on L. leucocephala growth differed between the Se forms (selenate and selenite) supplied in the soil. Selenate was prejudicial to plants grown in the soil with low P dose, while selenite was harmful to plants grown in soil with high P dose. The decreasing soil S dose increased the toxic effect of Se in L. leucocephala plants. Se tissue concentration and total Se accumulation in L. leucocephala shoot were higher with selenate supply in the soil when compared with selenite. Therefore, selenite proved to be less phytoavailable in the weathered tropical soil and, at the same time, more toxic to L. leucocephala plants than selenate. Thus, it is expected that L. leucocephala plants are more efficient to phytoextract and accumulate Se as selenate than Se as selenite from weathered tropical soils, for either strategy of phytoremediation (decontamination of Se-polluted soils) or purposes of biofortification for animal feed (fertilization of Se-poor soils).

     

Contamination status and potential release of trace metals in a mangrove forest sediment in Ho Chi Minh City,Vietnam

Can Gio district is located in the coastal area of Ho Chi Minh City, southern Vietnam. Discharge of wastewater from Ho Chi Minh City and neighboring provinces to the rivers of Can Gio has led to concerns about the accumulation of trace metals (As, Cu, Cr, Ni, Pb, and Zn) in the coastal sediments. The main objective of this study was to assess the distribution of As, Cu, Cr, Ni, Pb, and Zn in surface and core sediments and to evaluate the contamination status in relation to local background values, as well as the potential release of these selected trace metals from sediments to the water environment. Sediment characteristization, including determination of fine fraction, pH, organic matter, and major elements (Al, Fe, Ca, K, Mg, and S), was carried out to investigate which parameters affect the trace metal enrichment. Fine fraction and Al contents were found to be the controlling proxies affecting the distribution of trace metals while other sediment characteristics did not show any clear influence on trace metals’ distribution. Although As concentrations in the sediments were much higher compared to its reference value in other areas, the enrichment factor based on local background values suggests minor contamination of this element as well as for Cr, Cu, and Pb. Risk assessment suggested a medium to very high risk of Mn, Zn, and Ni under acidification. Of importance is also that trace metals in sediments were not easily mobilized by organic complexation based on their low extractabilities by ammonium-EDTA extraction.

     

Natural phillipsite as a matrix for a slow-release formulation of oxamyl

The performance of phillipsite as a matrix for slow-release formulation of oxamyl [N,N-dimethyl-2-methylcarbamoyl-oxymino-2-(methylthio)acetamide] was tested. The adsorption kinetics followed a first-order law, and the adsorption isotherm fitted well in a two-surface Langmuir model, suggesting a double mechanism of interaction between oxamyl and the sorbent. The sorption mechanism, studied by FTIR, provided two fractions of oxamyl. The first one is sorbed on the mineral surface, linked by H-bonding, and the second one is constituted by a multilayer of oxamyl molecules linked by a water bridge between them. The release kinetics of oxamyl from a substratum zeolite-oxamyl also follows a first-order law, with two stages that correspond to both fractions of oxamyl previously detected.     

Passive air sampler as a tool for long-term air pollution monitoring: Part 1. Performance assessment for seasonal and spatial variations

The potential of passive air sampling devices (polyurethane foam disks) to assess the influence of local sources on the quality of the surrounding environment was investigated. DEZA Valasske Mezirici, a coal tar and mixed tar oils processing plant, and Spolana Neratovice, a chemical factory with the history of high production of organochlorinated pesticides (OCPs), were selected as the point sources of PAHs, and OCPs, respectively. Levels of PCBs, OCPs and PAHs were determined for all sampling sites and sampling periods. The study brought useful data about the air concentrations of POPs in the investigated regions. More important, it provided information on the transport and fate of POPs in the vicinity of local sources of contamination useful for the estimation of their influence. Very good capability of passive samplers to reflect temporal and spatial fluctuation in concentrations of persistent organic pollutants in the ambient air was confirmed which makes them applicable for monitoring on the local scale.     

Decolourization of synthetic dyes by Trametes hirsuta in expanded-bed reactors

The present paper studies the decolourization of different synthetic dyes (Indigo Carmine, Bromophenol Blue, Methyl Orange and Poly R-478) by the white-rot fungus Trametes hirsuta at bioreactor scale under solid-state conditions, operating with ground orange peelings as a support-substrate. Dye decolourization was performed in both batch and continuous mode. Batch cultivation led to high decolourization percentages in a short time (100% for Indigo Carmine in 3h and 85% for Bromophenol Blue in 7 h). As for continuous cultivation, different hydraulic retention times (HRT) were studied (0.8, 1, 1.5 and 3d). The highest decolourization percentages were obtained operating at a HRT of 3d, especially for the dyes Methyl Orange and Poly R-478 (81.4% and 46.9%, respectively). This is a very interesting result, since there are few studies dealing with the continuous decolourization of dyes at bioreactor scale by fungal laccases.     

Effect of chromium on the fatty acid composition of two strains of Euglena gracilis

The effect of hexavalent chromium on fatty acid composition was studied in two strains of Euglena gracilis; UTEX 753 (from the Culture Collection of Algae of Texas University, USA) and MAT (isolated from a highly polluted River). Both were grown in photoauxotrophic and photoheterotrophic conditions and exposed to two metal concentrations, one below and one above IC50. The high malondialdehyde (MDA) levels (3 to 7-fold) obtained with chromium concentration above IC50, suggested the existence of metal-induced lipid peroxidation. Total lipid content increased only with concentration below IC50, whereas it was inhibited by higher metal concentration. Photoheterotrophic control strains exhibited a significantly higher proportion of saturated and polyunsaturated fatty acids. Polyunsaturated acids were most affected by chromium, especially those related to chloroplast structures. Ultra-structure studies showed clear thylakoid disorganization in all treated cells. The results indicate that hexavalent chromium affects levels of fatty acids, especially those related to photosynthetic activity.     

Twentieth century overview of heavy metals in the Galician Rias (NW Iberian Peninsula)

The 18 Galician Rias, comprising 25% of the Iberian Peninsula coastline, form a unique system within the European continental Atlantic coast and provide a useful reference area for studies of metals. These rias are sensitive to anthropogenic influence due to the socioeconomic importance generated in these areas by industry, aquaculture, port activities, fishing, tourism and, accordingly, several islands lying within close proximity to the rias have recently been declared natural parks. Aquaculture in the Galician Rias is a growth industry and in 2000 the rias supported 3386 mussel rafts producing 2.5 x 10(8) kg year(-1), i.e. 40% of European Union total seafood production. The Galician Rias are partially stratified estuaries with positive residual circulation with fresh (runoff lower than 100 m3 s(-1) and salt water mixing inside the basins. This behaviour has direct consequences on metal fluxes whereby the rias behave as a barrier and accumulate metals in the sediments. Metals tend to deposit close to point sources and remobilization occurs inside the ria, leading to a seaward decrease in metal concentration. With the exception of the Ulla (Arosa Ria) and Eume (Ares-Betanzos Ria) head rivers and the Lagares river (Vigo Ria) the available data suggest that riverine freshwater inputs are not the main source of contamination. Metal studies reported in the literature mainly relate to Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, and to a lesser extent Hg and Sn. Studies of other harmful metals such as Ag, Se and As are notably lacking. In addition, the studies have been localized and mainly restricted to the surface sediment. Data of heavy metals in the dissolved phase, suspended particulate matter and biota is scarce in the mainstream literature and should be considered in the future research. From the entire Galician coast, data from seven rias of socio-economic importance form the bulk of the published work. There is an urgent need to standardize procedures, employ 'clean' procedures to avoid contamination of samples and regular assessment of analytical accuracy with CRMs in order that results can be compared among the scientific community and produce reliable results. The continuation of coastal environmental studies requires an enlargement of the sampling locations as well as systematic and periodic analysis of known pollution sources in order to decide whether coastal regeneration action is needed. Studies dedicated to metals in the water column are lacking and need more attention in future research. The majority of the available data correspond to the fluvial front (30%) at ria head and, to a lesser extent, to the oceanic front (3%), under summer upwelling events. Current awareness of the rias suggests that they are not contaminated although there is some evidence of important localized anthropogenically induced enrichments at the outflow of the Lagares River (Pb, Zn), the San Simón inlet (Pb) and near to the harbor (Pb, Zn, Cu) in the Vigo Ria, the inner part (Cu, Zn, Hg, Pb) of the Pontevedra Ria, the Ulla River estuary (Cu, Cr, Mn, Ni; Zn) in the Arosa Ria, the inner zone (Cu, Pb, Zn) of the Coru?a Ria, the Ferrol Ria (Zn) and the Eume Estuary (Zn, Mn, Ni, Co) in the Ares-Betanzos Ria. In addition, TBT enrichment has been found along the Galician coast, being highest in the industrial bays (Vigo, Coru?a and Ferrol). Nevertheless, it is important to point out the lack of information concerning the relationship between metal concentrations in different fractions of sediments and/or water and their bioavailability and toxicity on biota in order to confirm metal contamination dangers. The present paper reviews all the information published on metals in the rias up to the year 2000 and takes a biogeochemical standpoint, i.e. metal presence in the ria reservoirs: water column, suspended particulate matter, sediments and biota, as well as the fluvial and oceanic frontiers.