Treatment of a wastewater from a galvanizing industry containing chromium(VI) and zinc(II) by liquid surfactant membranes technique.

Galvanizing industries generate large amounts of effluents rich in toxic and carcinogenic chromium(VI) species. Effective and sustainable treatments are required to comply with environmental regulations. This work focused on the development of innovative treatments for Cr(VI) by its removal from a galvanizing industry wastewater (pHinitial = 5.9) containing Cr (78 mg.L-1) and Zn (2178 mg.L-1) using the liquid surfactant membranes technique. The membrane phase carrier was Alamine® 336 in Escaid™ 110. For a synthetic solution (Cr(VI) = 353mg.L-1, pHinternal phase = 1.5), 99.9% of Cr(VI) was extracted in three stages ([KOH]internal phase = 0.27 mol.L-1). For the galvanizing wastewater, two selective extractions treatments were proposed: (1) 87% of Cr(VI) and 2% of Zn(II) were extracted in a single stage ([HCl]feed phase = 0.03 mol.L-1, [KOH]internal phase = 0.6 mol.L-1); (2) 95.6% of Cr(VI) and practically no zinc were extracted in a single stage ([HCl] feed phase = 10-6mol.L-1, [HCl] internal phase = 5mol.L-1). In another treatment condition ([HCl] feed phase = 2mol.L-1 and [KOH] internal phase = 1.2 mol.L-1), the simultaneous Cr(VI) and Zn(II) extractions (95% and 70%, respectively) were obtained in a single stage and more than 99% of both metals in three stages. This resulted in a depleted feed phase with 0.01 mg.L-1 of Cr(VI), that allows its discharge, according to the Brazilian legislation (≤0.1 mg/L).

Pharmacokinetic behavior of enrofloxacin and its metabolite ciprofloxacin in urutu pit vipers (Bothrops alternatus) after intramuscular administration.

Enrofloxacin is widely used in veterinary medicine and is an important alternative to treating bacterial infections, which play an important role as causes of disease and death in captive snakes. Its extralabel use in nontraditional species has been related to its excellent pharmacokinetic and antimicrobial characteristics. This can be demonstrated by its activity against gram-negative organisms implicated in serious infectious diseases of reptile species with a rapid and concentration-dependent bactericidal effect and a large volume of distribution. Pharmacokinetic parameters for enrofloxacin were investigated in seven urutu pit vipers (Bothrops alternatus), following intramuscular injections of 10 mg/kg. The plasma concentrations of enrofloxacin and its metabolite, ciprofloxacin, were measured using high-performance liquid chromatography. Blood samples were collected from the ventral coccygeal veins at 0.5, 1, 2, 4, 8, 12, 24, 36, 48, 72, 96, 108, and 168 hr. The kinetic behavior was characterized by a relatively slow absorption (time of maximal plasma concentration = 4.50 +/- 3.45 hr) with peak plasma concentration of 4.81 +/- 1.12 microg/ml. The long half-life during the terminal elimination phase (t1/2 lambda = 27.91 +/- 7.55 hr) of enrofloxacin after intramuscular administration, calculated in the present study, could suggest that the antibiotic is eliminated relatively slowly and/or the presence of a slow absorption in urutu pit vipers. Ciprofloxacin reached a peak plasma concentration of 0.35 microg/ml at 13.45 hr, and the fraction of enrofloxacin metabolized to ciprofloxacin was 13.06%. If enrofloxacin's minimum inhibitory concentration (MIC90) values of 0.5 microg/ml were used, the ratios AUC(e+c): MIC90 (276 +/- 67 hr) and Cmax(e+c): MIC90 (10 +/- 2) reach the proposed threshold values (125 hr and 10, respectively) for optimized efficacy and minimized resistance development when treating infections caused by Pseudomonas. The administration of 10 mg/kg of enrofloxacin by the i.m. route should be considered to be a judicious choice in urutu pit vipers against infections caused by microorganisms with MIC values < or = 0.5 microg/ml. For less susceptible bacteria, a dose increase and/or an interval reduction should be evaluated.

Evaluation of heavy metals and arsenic speciation discharged by the industrial activity on the Tinto-Odiel estuary, SW Spain.

This study reports the annual amount of heavy metals discharged by industrial activity into the estuary of the Ría of Huelva (SW Spain). The findings showed that the discharged metals found in highest amounts were Fe (11 t y⁻¹), Zn (3.4 t y⁻¹) and Mo (0.88 t y⁻¹). There were other metals with high pollutant charge, such as Ti (232 kg y⁻¹), As (228 kg y⁻¹), Ni (195 kg y⁻¹), Pb (100 kg y⁻¹), Cr (39 kg y⁻¹) and Cd (33 kg y⁻¹). These results were compared with pollutants transported via the Tinto and Odiel rivers from abandoned mining activities in the Iberian Pyrite Belt (IPB), and it was deduced that the amounts spilled exclusively by industries were less than 1% in relation to the total discharge. Hence, the treatment of residues from the IPB should be the priority goal to improve water quality in the estuary.

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain.

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.

Development of a rapid extraction procedure for speciation of arsenic in chicken meat.

A rapid extraction procedure has been developed for speciation of arsenic in chicken tissue. Water, methanol-water (1:1), and methanol-chloroform (1:1) were tested as extraction media. Individual use of an ultrasonic bath, a microwave oven, or an ultrasonic probe was not sufficient for quantitative recovery of As(III), dimethylarsinate, monomethylarsonate, As(V), and arsenobetaine in spiked samples of chicken tissue. A new extraction procedure using a methanol-water mixture and a microwave oven then an ultrasonic probe enabled extraction of the arsenic species in 7 min with efficiencies ranging from 80 to 100%. HPLC-UV-HG-AFS was used for the determinations. The extraction procedure was 100% efficient when applied to real samples of chicken tissue. AsB (48+/-5 microg As kg (-1)) and one containing-arsenic feed additive, Nitarsone (227+/-5 microg As kg (-1)) were detected.

Preservation procedures for arsenic speciation in a stream affected by acid mine drainage in southwestern Spain.

A preservation study has been performed for arsenic speciation in surface freshwaters affected by acid mine drainage (AMD), a pollution source characterized by low pH and high metallic content. Two sample preservation procedures described in the literature were attempted using opaque glass containers and refrigeration: i) addition of 0.25 mol L(-1) EDTA to the samples, which maintained the stability of the arsenic species for 3 h; and ii) in situ sample clean-up with a cationic exchange resin, in order to reduce the metallic load, which resulted in a partial co-adsorption of arsenic onto Fe precipitates. A new proposed method was also tried: sample acidification with 6 mol L(-1) HCl followed by in situ clean-up with a cationic exchange resin, which allowed a longer preservation time of at least 48 h. The proposed method was successfully applied to water samples with high arsenic content, taken from the Aguas Agrias Stream (Odiel River Basin, SW Spain), which is severely affected by AMD that originates at the nearby polymetallic sulfide mine of Tharsis. The speciation results obtained by liquid chromatography-hydride generation-atomic fluorescence spectrometry (HPLC-HG-AFS) indicated that during the summer the main arsenic species was As(V) at the hundred microg L(-1) level, followed by DMA (dimethyl arsenic) and As(III) below the ten microg L(-1) level. In winter, As(V) and As(III) increased at least fivefold, whereas the DMA was not detected.

Extraction procedures for chemical speciation of arsenic in atmospheric total suspended particles.

An arsenic chemical speciation study was performed in 2000, using air filters on which total suspended particles (TSP) were collected, from the city of Huelva, a medium size city with huge industrial influence in SW Spain. Different procedures for extraction of the arsenic species were performed using water, NH2OH.HCl, and H3PO4 solutions, with either microwave or ultrasonic radiation. The best optimised extraction methods were use of 100 mmol L(-1) NH2OH.HCl and 10 mmol L(-1) H3PO4 and microwave radiation for 4 min. High-performance liquid chromatography coupled with hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) was employed for determination of the arsenic species. The results from 12 TSP air filters collected on a monthly basis showed extraction was quantitative (94% with NH2OH.HCl and 86% H3PO4). Only inorganic arsenic species (arsenite and arsenate) were detected. The mean arsenite concentration was 1.2+/-0.3 ng m(-3) (minimum 0.3 ng m(-3), maximum 1.8 ng m(-3)). The mean arsenate concentration was 10.4+/-1.8 ng m(-3), with greater monthly variations than arsenite (minimum 2.1 ng m(-3), maximum 30.6 ng m(-3)). The high level of arsenic species in the TSP samples can be related to a copper smelter located in the region.