Growth, photosynthetic and respiratory responses to sub-lethal copper concentrations in Scenedesmus incrassatulus (Chlorophyceae)

In the present paper we investigated the effects of sub-lethal concentrations of Cu²⁺ in the growth and metabolism of Scenedesmus incrassatulus. We found that the effect of Cu²⁺ on growth, photosynthetic pigments (chlorophylls and carotenoids) and metabolism do not follow the same pattern. Photosynthesis was more sensitive than respiration. The analysis of chlorophyll a fluorescence transient shows that the effect of sub-lethal Cu²⁺ concentration in vivo, causes a reduction of the active PSII reaction centers and the primary charge separation, decreasing the quantum yield of PSII, the electron transport rate and the photosynthetic O₂ evolution. The order of sensitivity found was: Growth > photosynthetic pigments content = photosynthetic O₂ evolution > photosynthetic electron transport > respiration. The uncoupled relationship between growth and metabolism is discussed.     

Structure of Mn-Zr mixed oxides catalysts and their catalytic performance in the gas-phase oxidation of chlorocarbons

The catalytic activity and selectivity of manganese zirconia mixed oxides were evaluated for the oxidation of two common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane (DCE) and trichloroethylene (TCE). Mixed oxides with varying Mn-Zr content were prepared by coprecipitation via nitrates, and subsequent calcination at 600 degrees C for 4 h in air. These catalysts were characterised by means of several techniques such as atomic emission spectrometry, N2 adsorption-desorption, powder X-ray diffraction, temperature-programmed desorption of ammonia, pyridine adsorption followed by diffuse reflectance infrared spectroscopy and temperature-programmed reduction with hydrogen. The active catalytic behaviour of Mn-Zr mixed oxides was ascribed to a substantial surface acidity combined with readily accessible active oxygen species. Hence, the mixed oxide with 40 mol% manganese content was found to be an optimum catalyst for the combustion of both chlorocarbons with a T50 value around 305 and 315 degrees C for DCE and TCE oxidation, respectively. The major oxidation products were carbon dioxide, hydrogen chloride and chlorine. It was observed that the formation of both CO2 and Cl2 was promoted with Mn loading.     

Removal of a broad range of surfactants from municipal wastewater--comparison between membrane bioreactor and conventional activated sludge treatment

Elimination of alkylphenol ethoxylates (APEO) and their degradation products (alkylphenols and alkylphenoxy carboxylates), as well as linear alkylbenzene sulfonates (LAS) and coconut diethanol amides (CDEA), was studied in a pilot plant membrane bioreactor (MBR) working in parallel to a full-scale wastewater treatment plant (WWTP) using conventional activated sludge (CAS). In the CAS system 87% of parent long ethoxy chain NPEOs were eliminated, but their decomposition yielded persistent acidic and neutral metabolites which were poorly removed. The elimination of short ethoxy chain NPEOs (NP(1)EO and NP(2)EO) averaged 50%, whereas nonylphenoxy carboxylates (NPECs) showed an increase in concentrations with respect to the ones measured in influent samples. Nonylphenol (NP) was the only nonylphenolic compound efficiently removed (96%) in the CAS treatment. On the other hand, MBR showed good performance in removing nonylphenolic compounds with an overall elimination of 94% for the total pool of NPEO derived compounds (in comparison of 54%-overall elimination in the CAS). The elimination of individual compounds in the MBR was as follows: 97% for parent, long ethoxy chain NPEOs, 90% for short ethoxy chain NPEOs, 73% for NPECs, and 96% for NP. Consequently, the residual concentrations were in the low mug/l level or below it. LAS and CDEA showed similar elimination in the both wastewater treatment systems that were investigated, and no significant differences were observed between the two treatment processes. Nevertheless, for all studied compounds the MBR effluent concentrations were consistently lower and independent of the influent concentrations. Additionally, MBR effluent quality in terms of chemical oxygen demand (COD), NH(4)(+) concentration and total suspended solids (TSS) was always superior to the ones of the CAS and also independent of the influent quality, which demonstrates high potential of MBRs in the treatment of municipal wastewaters.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part I. Application to surface, waste and indirect discharge water samples in Austria

A method for simultaneous quantitative determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds (QACs) has been developed, validated and subsequently applied to real water samples in Austria. The method employs liquid-liquid extraction (LLE) followed by liquid chromatography/tandem mass spectrometry (LC-MS/MS), using electrospray ionization (ESI) in positive mode. The overall method quantification limits range from 4 to 19ng/L for the enrichment of 500mL water samples and analyte recoveries are between 80 and 99%. The method was applied to 62 of the respective water samples without filtration to avoid the loss of the analytes due to the high adsorption capacity of these compounds. Maxima in the mg/L range, especially in the wastewater of hospitals and laundries, could be detected for the selected target compounds.     

Influence of urbanization and tourist activities on the water quality of the Potrero de los Funes River (San Luis – Argentina)

A study of the water quality of the Potrero de los Funes River (San Luis – Argentina) was carried out in order to evaluate the possible effect of the anthropogenic activities on the river developed in the homonymous town. Samples were collected during the period March 2000–November 2005 at three selected sampling sites (RP₁, RP₂ and RP₃). Different physicochemical and bacteriological parameters (turbidity, pH, conductivity, suspended solids, alkalinity, potassium, sodium, calcium, magnesium, chlorides, nitrates, phosphates, sulphates, chemical oxygen demand (COD), 5-day biological oxygen demand (BOD₅), dissolved oxygen, total coliforms, Escherichia coli and total heterotrophic bacteria) were analysed according to the Standard Method for the Examination of Water and Wastewater. When comparing the values of total coliforms, E. coli, total heterotrophic bacteria, COD, BOD₅ and phosphates from the zone without anthropogenic influence (RP₁) and the urban zones (RP₂ and RP₃) an important variation in the parameters was observed. These results indicate that the urban activity produces a serious and negative effect on the water quality, thus constituting a sanitary risk and may have a major impact on the trophic status of the Potrero de los Funes dam. As case study, we report on the use of General Quality Index (GQI) to evaluate spatial and seasonal changes in the water quality of Potrero de los Funes River. Results revealed a significant degradation of the water quality at RP₂ and RP₃.     

Antimony distribution and mobility in topsoils and plants (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa) from polluted Sb-mining areas in Extremadura (Spain)

A study about topsoil antimony distribution and mobility from the soils to the biomass has been afforded in three abandoned Sb mining areas located at Extremadura. Physico-chemical characteristics of the soils and total antimony levels were measured in soils and autochthonous plant species (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa). Comparison with corresponding values in reference areas isolated from the mining activities is discussed. Antimony mobility in the soils was estimated by measuring the water extractable fraction; low results were obtained for the three soil areas, with no statistical differences. Plant ability to accumulate antimony was estimated by use of plant accumulation coefficients (PAC). Seasonal (spring vs. autumn) effects on the antimony content in the plant species. Cytisus striatus from Mari Rosa mine presented antimony excluder characteristics, whereas Dittrichia viscosa specimens growing in San Antonio mine showed a significant antimony bioaccumulation.     

Semi-parametric statistical approaches for space-time process prediction

The problem of estimation and prediction of a spatial-temporal stochastic process, observed at regular times and irregularly in space, is considered. A mixed formulation involving a non- parametric component, accounting for a deterministic trend and the effect of exogenous variables, and a parametric component representing the purely spatio-temporal random variation is proposed. Correspondingly, a two-step procedure, first addressing the estimation of the non- parametric component, and then the estimation of the parametric component is developed from the residual series obtained, with spatial-temporal prediction being performed in terms of suitable spatial interpolation of the temporal variation structure. The proposed model formula-tion, together with the estimation and prediction procedure, are applied using a Gaussian ARMA structure for temporal modelling to space-time forecasting from real data of air pollution concentration levels in the region surrounding a power station in northwest Spain.     

Performance evaluation of two commercial chemiluminescence NOx analysers according to European Standard EN 14211

According to Directive 2008/50/EC, all equipment used for NO(x) fixed measurements must comply with the reference method or equivalent by 11 June 2013. Up to that date, non-type-approved equipment can continue to be used in air monitoring networks and will probably also be used in air pollution studies even after that date. In this context, it is advisable to know how these "old" measuring instruments respond to the requirements of European Standard EN 14211: 2005: Ambient Air Quality--Standard method for the measurement of the concentration of nitrogen dioxide and nitrogen monoxide by chemiluminescence. In this work, we carry out a thorough performance evaluation of two commercial NO(x) analysers, both purchased before 2010, according to the mentioned Standard. Results show that water vapour interference is one of the most important disconformities with this Standard. The expanded uncertainty estimation of both analysers was below the quality objective of the above-mentioned Directive (15%); however, this calculation was performed by applying some modifications to the proposed model of Standard EN 14211. These modifications are also discussed in the paper.     

Prediction models of CO, SPM and SO2 concentrations in the Campo de Gibraltar Region, Spain: a multiple comparison strategy

The 'Campo de Gibraltar' region is a very industrialized area where very few air pollution studies have been carried out. Up to date, no model has been developed in order to predict air pollutant levels in the different towns spread in the region. Carbon monoxide (CO), Sulphur dioxide (SO(2)) and suspended particulate matter (SPM) series have been investigated (years 1999-2000-2001). Multilayer perceptron models (MLPs) with backpropagation learning rule have been used. A resampling strategy with two-fold crossvalidation allowed the statistical comparison of the different models considered in this study. Artificial neural networks (ANN) models were compared with Persistence and ARIMA models and also with models based on standard Multiple Linear Regression (MLR) over test sets with data that had not been used in the training stage. The models based on ANNs showed better capability of generalization than those based on MLR. The designed procedure of random resampling permits an adequate and robust multiple comparison of the tested models. Principal component analysis (PCA) is used to reduce the dimensionality of data and to transform exogenous variables into significant and independent components. Short-term predictions were better than medium-term predictions in the case of CO and SO(2) series. Conversely, medium-term predictions were better in the case of SPM concentrations. The predictions are significantly promising (e.g., d (SPM 24-ahead) = 0.906, d (CO 1-ahead) = 0.891, d (SO2 1-ahead) = 0.851).     

Pollution by organochlorine pesticides in Navachiste-Macapule,Sinaloa, Mexico

The lagoon system of Navachiste-Macapule is located in northern Mexico, in the state of Sinaloa, with an area of 24,000 ha. The main economic activity in the area is agriculture, and the lagoon lies next to the irrigation district ID-063 which covers 116,615 ha. The purpose of this study is to evaluate the levels of pollution generated by organochlorine pesticides (OC) in the surface sediments of the lagoon and in the agricultural drains of the ID-063 that are supposedly transported into the system as a result of agricultural activities and runoff from adjacent land. For this, between 2006 and 2007, 45 surface sediment samples were collected (warm dry, rainy and cold dry) from 15 sampling sites, during the three climatic seasons. Of these, eight were located inside the lagoon in marine conditions (salinity >31 PSU) and seven in the agricultural drains of the ID-063 in freshwater conditions (salinity <5 PSU). The average concentration of the OC in the sediments was 44.75 ng g^− 1, among which the group of the alicyclic compounds presented the greatest concentrations. The average value of the total organic carbon (TOC) in the sediments of the system was 0.90%. The sediments collected inside the lagoon had an average OC concentration of 18.97 ng g^− 1, and the predominant type of sediment was fine to very fine sand. The average OC concentration in the sediments collected in the agricultural drains was 75.69 ng g^− 1, where fine sediments (silt) were predominant. The presence of methoxychlor, endrin and heptachlor suggested that these compounds were continuously used in the system, even though their use is forbidden in Mexico.