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Abstract:In the present study, several pre-polymerized coagulants of iron and aluminum were tested for their efficiency towards As(V) and As(III) removal from water sources. The results showed that the pre-polymerized coagulants of iron, such as poly-ferric sulfate and poly-ferric silicate chloride, were very efficient for As(V) removal. With regard to As(III) removal, among all examined coagulants, including the conventional ferric chloride, only the poly-ferric sulfate (PFS) was able to reduce As(III) to concentrations below the drinking water regulation limit of 10 µg/L. In contrast, all tested composite coagulants based on aluminum were not capable of removing efficiently both species of arsenic. PFS addition in water containing 4 mM of alkalinity and 25 µg/L of As(V) and As(III) (i.e., total arsenic concentration 50 µg/L) resulted in finished water with less than 5 µg/L arsenic, only by dosing 5 mg Fe-PFS/L at pH 7, whereas, simultaneously, the residual iron concentration was found well below its drinking water regulation limit of 200 µg/L. The use of PFS could provide a viable alternative for As(III) and As(V) removal at household treatment level for application in vulnerable communities, without the need of any additional treatment, such as oxidation of As(III) to As(V).

Arsenic (As) and chromate (Cr(VI)) contamination of ground and surface waters is a major problem worldwide. Given that a new drinking water limit is anticipated for Cr(VI) and that the limit of arsenic in drinking water is quite low (10 μg/L), there is an urgent need for evaluating technologies that could be efficient for removal of both contaminants simultaneously. In this work, the use of Fe(II) redox assisted coagulation was investigated to simultaneously remove the contaminants of interest. The basic principle of this technology is that Fe(II) could react with Cr(VI) and form Fe(III)-hydroxides and insoluble Cr(III) species, while the freshly formed Fe(III) hydroxides are very efficient adsorbents for As(V). The effect of pH, the water matrix composition, Fe(II) dose, initial contaminant concentrations, NOM presence and phosphate concentration were the examined parameters. The results revealed that with a dose of 2 mg/L Fe(II), residual As(V) and Cr(VI) concentrations were both below 10 μg/L, from initial concentrations of 50 μg/L. Though, this is effective only at circumneutral pH values. This is however not a big obstacle, since most natural waters, especially groundwaters, have near neutral pH values. At these pH values, residual iron concentration was far below 200 μg/L. The presence of phosphate anions inhibited As(V) removal but had no effect on Cr(VI) removal. Increasing Fe(II) concentrations eliminated the effect of phosphate and provided simultaneous phosphate removal. Therefore, Fe(II) coagulation can be applied, with secured results, for simultaneous As(V), Cr(VI) and phosphate removal from waters.

A headspace solid-phase microextraction (HS-SPME) method coupled to GC-MS was developed in order to determine trace levels of tetramethyltin (TeMT) and inorganic tin (iSn) after ethylation to tetraethyltin (TeET) in various matrices. The derivatization of iSn and the extraction of both TeMT and iSn as TeET were performed in one step. Sodium tetraethylborate (NaBEt(4)) was used as derivatization agent and the volatile derivatives were absorbed on a PDMS-coated fused silica fiber. The conditions for the HS-SPME procedure were optimized in order to gain in repeatability and sensitivity. Several critical parameters of GC-MS were also studied. The detection of TeMT and iSn as TeET peaks was performed by the SIM mode. The precision of the proposed method is satisfactory providing RSD values below 10% for both tin species and good linearity up to 10 microg/L. The developed method was successfully applied to the determination of tin species in several samples like canned fish, fish tissues, aquatic plants, canned mineral water and sea water. The proposed HS-SPME-GC-MS method was proved suitable to monitor the concentration levels of toxic tin compounds in environmental and biological samples.

A headspace solid-phase micro-extraction (HS-SPME) method was employed in order to study the effect of storage conditions of human urine samples spiked with tributyltin (TBT) using gas chromatography and mass spectrometry. To render the analyte more volatile, the derivatization (ethylation) was made in situ by sodium tetraethylborate (NaBEt(4) ), which was added directly to dilute unpreserved urine samples and in buffers of similar acidity. The stability of TBT in human urine matrix was compared with the stability of TBT in buffer solutions of similar pH value. Critical parameters of storage conditions such as temperature and time, which affect the stability of TBT in this kind of matrix, were examined extensively. The tests showed that the stability of TBT remains practically satisfactory for a maximum of 2 days of storage either at +4 or 20°C. Greater variations were observed in the concentration of TBT in human urine samples at +4°C and lower ones at -20°C over a month's storage. The freeze-thaw cycles have negative effect on the stability and should be kept to a minimum. The results from spiked urine samples are also discussed in comparison to those acquired from buffer solutions of equal TBT concentration.