How sulfur species can accelerate the biological immobilization of the toxic selenium oxyanions and promote stable hexagonal Se0 formation.

Toxic selenium oxyanions and sulfur species are often jointly present in contaminated waters and soils. This study investigated the effect on kinetics and resulting products for bio-reduction of selenium oxyanions in the presence of biologically produced sulfur resulting from bio-oxidation of sulfide in (bio)gas-desulfurization (bio-S0) and of sulfate. Selenite and selenate (~2 mmol L-1) bio-reduction was studied in batch up to 28 days at 30 oC and pH 7 using lactic acid and a sulfate-reducing sludge, 'Emmtec'. Bio-S0 addition increased the selenite removal rate, but initially slightly decreased selenate reduction rates. Selenite reacted with biologically generated sulfide resulting in selenium-sulfur, which upon further bio-reduction creates a sulfur bio-reduction cycle. Sulfate addition increased the bio-reduction rate for both selenite and sulfate. Bio-S0 or sulfate promoted hexagonal selenium formation, whereas without these, mostly amorphous Se0 resulted. With another inoculum, 'Eerbeek', bio-S0 accelerated the selenite reduction rate less than for 'Emmtec' because of lower sulfur and higher selenite bio-reduction rates. Bio-S0 addition increased the selenate reduction rate slightly and accelerated hexagonal selenium formation. Hexagonal selenium formation is advantageous because it facilitates separation and recovery and is less mobile and toxic than amorphous Se0. Insights into the interaction between selenium and sulfur bio-reduction are valuable for understanding environmental pathways and considerations regarding remediation and recovery.

High-rate biological selenate reduction in a sequencing batch reactor for recovery of hexagonal selenium.

Recovery of selenium (Se) from wastewater provides a solution for both securing Se supply and preventing Se pollution. Here, we developed a high-rate process for biological selenate reduction to elemental selenium. Distinctive from other studies, we aimed for a process with selenate as the main biological electron sink, with minimal formation of methane or sulfide. A sequencing batch reactor, fed with an influent containing 120 mgSe L-1 selenate and ethanol as electron donor and carbon source, was operated for 495 days. The high rates (419 ± 17 mgSe L-1 day-1) were recorded between day 446 and day 495 for a hydraulic retention time of 6 h. The maximum conversion efficiency of selenate amounted to 96% with a volumetric conversion rate of 444 mgSe L-1 day-1, which is 6 times higher than the rates reported in the literature thus far. At the end of the experiment, a highly enriched selenate reducing biomass had developed, with a specific activity of 856 ± 26 mgSe-1day-1gbiomass-1, which was nearly 1000-fold higher than that of the inoculum. No evidence was found for the formation of methane, sulfide, or volatile reduced selenium compounds like dimethyl-selenide or H2Se, revealing a high selectivity. Ethanol was incompletely oxidized to acetate. The produced elemental selenium partially accumulated in the reactor as pure (≥80% Se of the total mixture of biomass sludge flocs and flaky aggregates, and ~100% of the specific flaky aggregates) selenium black hexagonal needles, with cluster sizes between 20 and 200 µm. The new process may serve as the basis for a high-rate technology to remove and recover pure selenium from wastewater or process streams with high selectivity.

Adjuvant intraoperative photodynamic therapy diminishes the rate of local recurrence in a rat mammary tumour model.

The use of photodynamic therapy (PDT) as an adjunct to curative tumour resection was investigated in a tumour recurrence model, using rat mammary adenocarcinoma BN472. Tumours were inoculated subcutaneously in 60 animals and resected after 21 days of growth. Immediately after removal, the operation site was exposed to 320-450 nm light of 0.1 W cm-2 and 60 J cm-2 after photosensitisation with either Photofrin (5 mg kg-1 i.v. 48 h before illumination) or 5-aminolaevulinic acid (ALA) (2 mg ml-1 in drinking water for 9 days). Porphyrin concentrations were measured in tissue samples. After 28 days, animals treated with adjunctive PDT had a significantly longer tumour-free interval than controls (P < 0.01); median 25 days (Photofrin), 18 days (ALA), 14 days (controls). Moreover, in the PDT groups significantly fewer rats had lymph node metastasis. A prophyrin concentration ratio between tumour and mammary tissue of 2:1 was found after Photofrin and 4:1 after ALA. The results indicate that adjuvant intraoperative PDT may be a safe and effective method of destroying residual tumour, thereby preventing locoregional tumour recurrence.