Temporal evolution of linear alkylbenzene sulfonates and heavy metals in sludge from wastewater treatment plant.

Five homologues of linear alkylbenzene sulfonates (LAS)-LAS C-10, LAS C-11, LAS C-12, and LAS C-13 and total LAS-were monitored during a one-year period in primary, secondary, and digested sludge to evaluate their presence and temporal evolution. Extraction of LAS was carried out using microwaves energy, and determination was performed using high-performance liquid chromatographic- fluorescence (HPLC-FL). The results showed that concentrations of total LAS were between 9 337 mg/kg(-1) dry matter for primary sludge and 33.3 mg/kg(-1)(DM) for secondary sludge. Concentrations of total LAS were greater than 2 113 mg/kg(-1) in primary and digested sludge and were less than 260 mg/kg(-) in secondary sludge. On the other hand, the highest concentrations of LAS in primary sludge were found in summer, probably because of lack of rain during those months. Concentrations tend to be constant throughout the year in digested sludge. In addition heavy metals also were analyzed. Heavy metals, including zinc, copper, nickel, lead, and chromium are persistent environmental contaminants that cannot be destroyed. Biomagnification through the food-chain and potential accumulation in human tissues can cause both human health and environmental concerns. Concern regarding total heavy metal content of sludge limits sludge recycling for use on agricultural lands. This paper presents a comparative study of wastewater sludge that are going to be used as fertilizer based on the requirements of legislation proposed in the European Union. This research found that concentrations of total LAS in digested sludge are higher than the limits established in the proposed new draft.

New rapid methods for determination of total LAS in sewage sludge by high performance liquid chromatography (HPLC) and capillary electrophoresis (CE).

Linear alkylbenzene sulfonates (LAS) are the most common synthetic anionic surfactant used in domestic and industrial detergents, with a global production of 2.4x10(6) t year(-1). After use and disposal, LAS may enter the environment by one of the several routes, including by direct discharge to surface water or discharge to water from sewage treatment plants. Sewage treatment plants break down LAS only partly: some of them remain in effluent and other fraction is adsorbed in sewage solid. New and rapid methods for determination of total LAS from sewage sludge based on microwave assisted extraction and HPLC-FL and CE-DAD determination are proposed. The extraction of total LAS is carried out by using microwaves energy, an extraction time of 10 min and 5 mL of methanol. For HPLC-FL determination, mobile phase acetonitrile-water was used, comprising 60% (v/v) from 0 to 1 min and a flow rate of 1 mL min(-1) programmed to 100% acetonitrile between 1 and 2 min and a flow rate of 2 mL min(-1). The final composition was maintained for a further 5 min. The determination of total LAS by CE-DAD was performed in a phosphate buffer (10 mM, pH 9). The separation voltage was 25 kV and the temperature of the capillary was 30 degrees C. Injections were performed in the pressure mode and the injection time was set at 12 s. The determination of total LAS is carried out in less than 5 min. The methods did not require clean-up or preconcentration steps. Detection limit for total LAS in the sludge was 3.03 mg kg(-1) using HPLC-FL and 21.0 mg kg(-1) using CE-DAD, and recoveries were >85% using both determination methods. Concentrations of total LAS obtained using both methods were compared with the sum of concentrations of homologues LAS C-10, LAS C-11, LAS C-12 and LAS C-13 obtained using microwaves assisted extraction and HPLC-FL and CE-DAD determination.

Optimization and validation of a new method for analysis of linear alkylbenzene sulfonates in sewage sludge by liquid chromatography after microwave-assisted extraction.

A new approach has been developed for the monitoring of linear alkylbenzene sulfonates (LAS) (C10-C13) in sewage sludge. It is based on microwave-assisted extraction (MAE) prior to high performance liquid chromatography coupled with diode array (HPLC-DAD) and fluorescence (HPLC-FL) detectors. Column Zorbax XDB-C8, 150 mm x 4.6 mm i.d., 5 microm particle size was used as well as acetonitrile-water containing 0.1 M NaClO4 (65:35) and isocratic elution. Compounds were isocratically eluted over 6 min runtime at a flow rate of 1 mL min(-1). Since polar interferences are eluted between 0 and 2 min, they do not interfere in the analysis. The column was thermostated at a temperature of 25 degrees C. For the determination of LAS, DAD-UV (lambda(ex) = 225 nm) and fluorescence (lambda(ex) = 225 nm, lambda(em) = 295 nm) detectors were employed. The main factors affecting the extraction efficiency (extractant volume, microwave power and irradiation time) were optimized using a compost sludge. The detection limit for total LAS in the sludge was < 5 mg kg(-1). The extraction of C10-C13 homologues is carried out by using an extraction time of 10 min and 5 mL of methanol; whereas Soxhlet needs a 12 h extraction. The method did not require clean-up or preconcentration steps. Concentration levels of LAS were between 13,037 mg kg(-1) for digested sludge and 2492 mg kg(-1) for compost sludge.

Temporal evolution of polycyclic aromatic hydrocarbons (PAHs) in sludge from wastewater treatment plants: comparison between PAHs and heavy metals.

This paper presents results on the presence and temporal variability of the 16 PAHs recommended by the EPA in primary, secondary and digested sewage sludge over a year. The sewage sludges originated from the Guadalete wastewater treatment plant (WWTP) site in Jerez de la Frontera (Cádiz, Spain). These organic pollutants have been extracted from the sewage sludge by microwave energy. High performance liquid chromatography coupled with diode array (HPLC-DAD) or fluorescence (HPLC-FL) detectors have been used. The results showed that total PAHs concentration varied between 1,945 ng g(-1) dry matter (DM) for primary sludges collected in March and 10,100 ng g(-1) DM for primary sludge collected in June. Generally, concentrations of PAHs were higher in compost and digested sludge than in fresh one. On the other hand, the highest concentration of PAHs were found on summer. This thing is associated to the traffic increase from inland zones to the coast (Jerez de la Frontera is very near to beaches). Finally, this paper present a comparative study of the American an European legislation concluding that the limits of concentrations established are not exceeded. In addition heavy metals were analysed. The origin of PAHs and heavy metals seems to be different.

Spectrofluorimetric determination of velnacrine in human serum and urine.

A simple, sensitive and rapid spectrofluorimetric method to determine velnacrine, a cholinesterase inhibitor, has been developed and validated. The influence of pH, temperature, ionic strength, presence of excipients, metal ions and surfactants on the fluorescence intensity has been studied. The proposed method allows the determination of 5-100 ng ml(-1) of velnacrine in aqueous solution containing sodium acetate buffer (pH 5.6; 0.04 M) with lambda(excitation) 242 nm and lambda(emission) 359 nm. The detection and quantitation limits were 1.7 and 4.5 ng ml(-1) respectively. The method was successfully applied to the determination of velnacrine in human serum and urine.

A flow injection chemiluminescence method using Cr(III) as a catalyst for determining hydrogen peroxide. Application to H(2)O(2) determination in cultures of microalgae.

Flow injection analysis has been applied to the determination of hydrogen peroxide produced by some different species of microalgae. The method is based on the luminol-H(2)O(2) chemiluminescence reaction using Cr(III) as a catalyst. Optimum experimental conditions for the method have been studied and trace amounts of hydrogen peroxide determined with detection limits of 4 10(-8) mol/L. The method using Cr(III) was compared with that using horseradish peroxidase as the catalyst.

Electrochemical oxidation at carbon paste electrode of tacrine and 1-hydroxytacrine and differential pulse voltammetric determination of tacrine in pharmaceuticals and human urine.

The electrochemical oxidation of tacrine and its 1-OH-metabolite, has been studied by cyclic voltammetry and differential pulse voltammetry by using carbon paste electrodes. The peak current-concentration relationship was found to be linear up to 20 micrograms ml-1 with detection limits of 0.06 microgram ml-1 for tacrine and 0.18 microgram ml-1 for 1-OH-tacrine and quantitation limits of 0.20 microgram ml-1 for tacrine and 0.37 microgram ml-1 for 1-OH-tacrine. A method for determining tacrine by differential pulse voltammetry in pharmaceuticals and human urine, in the presence of 1-OH-tacrine, has been developed.

Spectrofluorimetric determination of cisatracurium and mivacurium in spiked human serum and pharmaceuticals.

Spectrofluorimetric methods to determine cisatracurium and mivacurium are proposed and applied to the determination of both substances in human serum and to the determination of mivacurium in pharmaceuticals. The fluorimetric methods allow the determination of 5-500 ng ml(-1) of mivacurium in aqueous solutions and 5-500 ng ml(-1) of cisatracurium in water-acetonitrile solutions, both containing acetic acid-sodium acetate buffer (pH 5.5) with lambda(exc)=230 nm and lambda(em)=324 nm.

Spectrofluorimetric determination of tacrine in pharmaceuticals and spiked human serum.

A spectrofluorimetric method to determine tacrine is proposed and applied to the determination of tacrine in human serum and pharmaceuticals. The fluorimetric method allows the determination of 1-70 ng ml-1 of tacrine in aqueous solutions containing acetic acid-sodium acetate buffer (pH 5.6) with lambda exc = 242 nm and lambda em = 362 nm.

Determination of beta-blocker drugs in pharmaceutical preparations by non-suppressed ion chromatography.

A rapid and feasible chromatographic method for determining atenolol, metoprolol, alprenolol, oxprenolol, acebutolol and propranolol by non-suppressed ion chromatography is proposed. The mobile phase consisted of 50 mM nitric acid in an aqueous solution of 4% (v/v) acetonitrile. Detection limits are in the range 0.1-2.7 mg l-1. The method was successfully applied to the determination of beta-blockers in several pharmaceutical formulations.