Integrated environmental factor-dependent growth and arsenic biotransformation by aquatic microalgae: A review.

Arsenic (As) is a toxic metalloid posing harming the human food chain through trophic transfer. Microalgae are primary producers, ensuring bioaccumulation and biogeochemical cycling of As in water environment. They are highly efficient at removing As from the environment, making these microscopic organisms eco-friendly and money saving method in As remediation process. However, microalgal growth and As biotransformation potential relies greatly on individual and integrated environmental factors. This review scrutinizes the available literature on the As biotransformation potentials of various marine and freshwater microalgae under individual and integrated stresses of such factors. Various combinations of important factors such as temperature, salinity, concentrations of As (V) and PO43─, pH, light intensity, and length of exposure period are summarized along with the optimum conditions for different microalgae. The effects of environmental factors on microalgal growth, changes in cell shape, and the relationship between As biotransformation and other activities are discussed in detail. Time-dependent As speciation pattern by aquatic microalgae are reviewed. Conceptual models highlighting the microalgal species particularly linked with environmental factor-dependent As biotransformation mechanisms are also summarized. This review will contribute to an in depth understanding of the connection between environmental factors, As uptake, and the biotransformation mechanism of marine and freshwater microalgae from the perspective of As remediation process.

A technique for the speciation analysis of metal-chelator complexes in aqueous matrices using ultra-performance liquid chromatography-quadrupole/time-of-flight mass spectrometry.

Chelators, capable of creating soluble complexes with metals, may disrupt the natural speciation of metals in environmental matrices. Detection of environmental speciation of such complexes has remained challenging as obtaining the precise inherent nature of metal-chelator complexes is difficult by using routine techniques. Herein, we report a rapid and sensitive technique for the speciation analysis of complexes of five metal ions (Ni, Pb, Co, Fe and Ca) with two aminopolycarboxylate chelator variants, namely, EDTA (ethylenediaminetetraacetic acid) and EDDS (ethylenediamine-N,N'-disuccinic acid), including the simultaneous quantification of those complexes. EDTA is characterized as environmentally persistent among the chelators used in the current work whereas EDDS is biodegradable. The speciation analysis was performed using ultra-performance liquid chromatography-quadrupole/time-of-flight mass spectrometry (UPLC-Q-TOF-MS). The separation was achieved by using hydrophilic interaction liquid chromatographic column. The effect of various operating parameters on analytes such as mobile-phase composition, buffer concentrations and pH, sample diluents, sample injection volume, and column temperature on the peak shape and sensitivity were systematically optimized. The dilution was the only requirement for preparing the samples for analysis. The average relative uncertainty was 2.4% with the average precision (as RSD, n= 7) of 3.5%. For the metal-EDTA complexes, LOD range was 3 to 76 nmol L-1 with satisfactory recovery from a simulated mix matrix (recovery: 79-97%) and river water by standard addition (recovery: 82-94%). For metal-EDDS complexes, LOD range was 66 to 293 nmol L-1 with recovery from a simulated mix matrix (recovery: 56-97%) and river water by standard addition (recovery: 61-91%). The proposed method will be applicable in speciation analysis and simultaneous detection of metal-chelator complexes from environmental samples.

Arsenic biotransformation potential of six marine diatom species: effect of temperature and salinity.

Temperature and salinity effects on marine diatom species growth has been studied extensively; however, their effect on arsenic (As) biotransformation has been imprecise. This study reports the growth, and As biotransformation and speciation patterns at various temperatures and salinities of six marine diatom species: Asteroplanus karianus, Thalassionema nitzschioides, Nitzschia longissima, Skeletonema sp., Ditylum brightwellii, and Chaetoceros didymus. The growth rate and As biotransformation potentials of these species during three weeks of culture in f/2 based medium were significantly affected by wide temperature (0-35 °C) and salinity (0.3-50‰) ranges. Growth and As biotransformation were higher at optimum temperatures of 10-25 °C, and salinity of 10-35‰, whereas growth and arsenic biotransformation were lower at <5 °C and 5‰ and >25 °C and 35‰, respectively. The results showed that As(V) to As(III) biotransformation differed significantly (p < 0.05) between day 10 and 17. At optimum temperature and salinity levels, the cell size and As biotransformation were higher for all the species. A conceptual model on temperature and salinity effects on growth and As uptake and biotransformation mechanisms by these species has been proposed based on the findings of this study.

Determination of multiple chelator complexes in aqueous matrices using ultra-performance liquid chromatography-quadrupole/time-of-flight mass spectrometry.

The determination of aminopolycarboxylate chelators in environmental samples has remained an analytical challenge due to the structural similarities of these species and their minute concentrations in such matrices. Herein, we report a fast and sensitive technique for the determination of multiple chelator complexes in an aqueous matrix using ultra-performance liquid chromatography-quadrupole/time-of-flight mass spectrometry (UPLC-Q-TOF-MS). Eight chelators, including non-biodegradable (EDTA, EDTAOH, GEDTA, DPTAOH and DTPA) and biodegradable (EDDS, GLDA, and MGDA) variants were examined after complexation with CuII. The detection of these species using reverse-phase chromatography was compared with that achieved with hydrophilic interaction chromatography based on the corresponding peak resolution and retention time. The effect of varying the composition and pH of the mobile phase on the corresponding peak profiles and intensities for the chelator complexes was also evaluated. The CuII-derivatives of the chelators were individually detected under the optimized operating conditions. Relative to high-performance liquid chromatography equipped with a photodiode array detector, the developed UPLC-Q-TOF-MS technique provides rapid determination of chelator complexes in aqueous matrices with high sensitivity and superior peak resolution. The limit of detection ranged from 1.7-36 nmol L-1, and the limit of quantification ranged from 5.7-120 nmol L-1 for the eight chelator complexes in solution. The coefficients of determination (R2) were 0.962-0.999 for the chelators with an average relative uncertainty of 2.2%. The method was validated using a simulated mixed matrix and river water by standard addition (recovery: 83-100%).