Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples

Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g⁻¹ for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g⁻¹). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.     

Joint use of data and modeling in coastal wave transformation

In the framework of a research project entitled ??BRISA??BReaking waves and Induced SAnd transport??, a methodology was devised to characterize the waves joining together in-situ measurements and numerical wave propagation models. With this goal in mind, a number of in-situ measurements were made, for selected positions in front of Praia de Faro (South Portugal), during four days (25th to 28th March, 2009) by using different types of equipments (e.g., resistive wave gauges, pressure sensors, currentmeters and a new prototype pore pressure sensor using optical fibre). Wave records were obtained simultaneously offshore (at a water depth of 11.7?m below mean sea level, MSL) and at the surf and swash zones. The data processing and analysis were made by applying classical time domain techniques. Numerical simulations of the wave propagation between offshore and inshore for the measurement period were performed with two numerical models, a 1D model based on linear theory and a nonlinear Boussinesq-type model, COULWAVE, both forced by the measured offshore wave conditions of 27th March 2009. Comparisons between numerical results and field data for the pressure sensors placed in the surf and swash zones were made and discussed. This approach enables to evaluate the performance of those models to simulate those specific conditions, but also to validate the models by gaining confidence on their use in other conditions.     

Sustainability: A Study of the Level of Ecological Behavior of Postgraduate Students in Brazil

The decline in the supply of natural resources is a cause for concern, especially given continued worldwide population growth. New habits and attitudes toward resource use are slowly being introduced into the everyday lives of persons residing in a number of countries. The term “ecological behavior” refers to acting in favor of the environment, whether these actions are voluntarily or not, or learned or not (Pato & Tamayo, 2006 ). The general objective of this study is to identify the environmental behavior—one of several terms used interchangeably with ecological behavior—of graduate students from a Brazilian federal institution of higher education. We chose this particular group because many of them already act, or will act, as professors. Thus, by virtue of their positions, they will function as opinion leaders who will influence the education of future professionals, establishing a chain through which shared values can gradually change the environmental behavior of society.     

Use of hairy roots extracts for 2,4-DCP removal and toxicity evaluation by Lactuca sativa test

2,4-Dichlorophenol (2,4-DCP) is widely distributed in wastewaters discharged from several industries, and it is considered as a priority pollutant due to its high toxicity. In this study, the use of different peroxidase extracts for 2,4-DCP removal from aqueous solutions was investigated. Tobacco hairy roots (HRs), wild-type (WT), and double-transgenic (DT) for tomato basic peroxidases (TPX1 and TPX2) were used to obtain different peroxidase extracts: total peroxidases (TPx), soluble peroxidases (SPx), and peroxidases ionically bound to the cell wall (IBPx). All extracts derived from DT HRs exhibited higher peroxidase activity than those obtained from WT HRs. TPx and IBPx DT extracts showed the highest catalytic efficiency values. The optimal conditions for 2,4-DCP oxidation were pH 6.5, H₂O₂ 0.5 mM, and 200 U mL^?1 of enzyme, for all extracts analyzed. Although both TPx extracts were able to oxidize different 2,4-DCP concentrations, the removal efficiency was higher for TPx DT. Polyethylene glycol addition slightly improved 2,4-DCP removal efficiency, and it showed some protective effect on TPx WT after 2,4-DCP oxidation. In addition, using Lactuca sativa test, a reduction of the toxicity of post removal solutions was observed, for both TPx extracts. The results demonstrate that TPx extracts from both tobacco HRs appear to be promising candidate for future applications in removing 2,4-DCP from wastewaters. This is particularly true considering that these peroxidase sources are associated with low costs and are readily available. However, TPx DT has increased peroxidase activity, catalytic efficiency, and higher removal efficiency than TPx WT, probably due to the expression of TPX1 and TPX2 isoenzymes.     

Mg-Fe layered double hydroxide with chloride intercalated: synthesis,characterization and application for efficient nitrate removal

Environmental Science and Pollution Research - Mg-Fe layered double hydroxide intercalated with chloride (Mg-Fe-Cl LDH) was synthetized, characterized, and evaluated as adsorbent to remove nitrate...     

Optical fiber based methodology for assessment of thiocyanate in seawater

A new methodology for the assessment of thiocyanate (SCN(-)) is proposed based on optical fiber (OF) detection coupled to a liquid chromatography system (LC). The developed methodology showed an adequate performance for the analysis of SCN(-) comparable to a high performance liquid chromatography with UV detector (HPLC-UV) methodology: a detection limit of 3 μg L(-1), a linear range from 4 to 400 μg L(-1), and an analytical time of less than 6 min. The OF based methodology was of compact design and easy operation. This simple system has the potential to be used as a sensing approach for SCN(-) in seawater.     

Particulate matter levels in a South American megacity: the metropolitan area of Lima-Callao,Peru

The temporal and spatial trends in the variability of PM₁₀ and PM_2.5 from 2010 to 2015 in the metropolitan area of Lima-Callao, Peru, are studied and interpreted in this work. The mean annual concentrations of PM₁₀ and PM_2.5 have ranges (averages) of 133–45 μg m^?3 (84 μg m^?3) and 35–16 μg m^?3 (26 μg m^?3) for the monitoring sites under study. In general, the highest annual concentrations are observed in the eastern part of the city, which is a result of the pattern of persistent local winds entering from the coast in a south-southwest direction. Seasonal fluctuations in the particulate matter (PM) concentrations are observed; these can be explained by subsidence thermal inversion. There is also a daytime pattern that corresponds to the peak traffic of a total of 9 million trips a day. The PM_2.5 value is approximately 40% of the PM₁₀ value. This proportion can be explained by PM₁₀ re-suspension due to weather conditions. The long-term trends based on the Theil-Sen estimator reveal decreasing PM₁₀ concentrations on the order of ?4.3 and ?5.3% year^?1 at two stations. For the other stations, no significant trend is observed. The metropolitan area of Lima-Callao is ranked 12th and 16th in terms of PM₁₀ and PM_2.5, respectively, out of 39 megacities. The annual World Health Organization thresholds and national air quality standards are exceeded. A large fraction of the Lima population is exposed to PM concentrations that exceed protection thresholds. Hence, the development of pollution control and reduction measures is paramount.     

OPTIMIZATION OF INTERMITTENT PUMPING SCHEDULES FOR AQUIFER REMEDIATION USING A GENETIC ALGORITHM1

ABSTRACT: Using a genetic algorithm (GA), optimal intermittent pumping schedules were established to simulate pump‐and‐treat remediation of a contaminated aquifer with known hydraulic limitations and a water miscible contaminant, located within the Duke Forest in Durham, North Carolina. The objectives of the optimization model were to minimize total costs, minimize health risks, and maximize the amount of contaminant removed from the aquifer. Stochastic ground water and contaminant transport models were required to provide estimates of contaminant concentrations at pumping wells. Optimization model simulations defined a tradeoff curve between the pumping cost and the amount of contaminant extracted from the aquifer. For this specific aquifer/miscible contaminant combination, the model simulations indicated that pump‐and‐treat remediation using intermittent pumping schedules for each pumping well produced significant reductions in predicted contaminant concentrations and associated health risks at a reasonable cost, after a remediation time of two years.     

Heavy metals in untreated/treated urban effluent and sludge from a biological wastewater treatment plant

Background, Aim and Scope

The presence of heavy metals in wastewater is one of the main causes of water and soil pollution. The aim of the present study was to investigate the removal of Cd, Cu, Pb, Hg, Mn, Cr and Zn in urban effluent by a biological wastewater treatment, as well as to quantify the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn, Tl, V and Zn in dewatering sludge from the Biological Wastewater Treatment Plant to Ribeirão Preto (RP-BWTP), Brazil.

Materials and Methods

Concentrations of Cd, Cr, Cu, Mn and Pb in wastewater and those of Ni in sludge were determined by atomic absorption spectrophotometry with graphite furnace atomization. Mercury concentrations in wastewater were measured by hydride generation atomic spectrophotometry, and Zn levels were determined by atomic absorption spectrophotometry using acetylene flame. In sludge, the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Sn, Tl, V and Zn were determined by inductively coupled plasma-mass spectrometry.

Results

The percentages of removal efficiency (RE) were the following: Hg 61.5%, Cd 60.0%, Zn 44.9%, Cu 44.2%, PB 39.7%, Cr 16,5% and Mn 10.4%. In turn, the mean concentrations (mg/kg) of metals in dewatering sludge followed this increasing order: Tl (<0.03), Hg (0.31), Be (0.43), As (1.14), Cd (1.34), V (59.2), Pb (132.1), Sn (166.1), Cr (195.0), Mn (208.1), Ni (239.4), Cu (391.7), Zn (864.4) and Fe (20537).

Discussion

The relationship between metal levels in untreated wastewater, as well as the removal efficiency are in agreement with previous data from various investigators, It is important to note that metal removal efficiency is not only affected by metal ion species and concentration, but also by other conditions such as operating parameters, physical, chemical, and biological factors.

Conclusions

Metal values recorded for treated wastewater and sludge were within the maximum permitted levels established by the Environmental Sanitation Company (CETESB), São Paulo, Brazil.

Recommendations

There is an urgent need for the authorities who are responsible for legislation on sludge uses in agriculture of establishing safety levels for As, Be, Hg, Sn, Tl and V.

Perspectives

According to the current metal levels, RP-BWTP sludge might be used for agriculture purposes. However, for an environmentally safe use of sewage sludge, further studies including systematic monitoring are recommended. Annual metal concentrations and predicted variations of those elements in the sludge should be monitored.