skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Autocalibration based on dilution of a single concentrated standard is used for the determination of silicate in sea water by the modified molybdenum blue method
The silicate (Si) molybdenum blue method was modified by combining oxalate and ascorbic acid into a single reagent and was used for determining Si in sea water samples. The first step of this automated assay protocol was designed to perform either a calibration by a single Si standard prepared in deionized (DI) water, or to dilute samples in the range of 0–160 μM Si to fit into 0–20 μM Si calibration range using a 20 cm flow cell. By designing the assay protocol to function in batch mode, the influence of salinity on calibration was eliminated, thus making the method suitable for analysis of samples collected in the open ocean, coastal areas, or rivers. Reproducibility and accuracy of this method were evaluated by analysis of certified sea water reference materials. Phosphate (P) does not interfere significantly if the Si:P ratio is 4:1 or larger. The limit of detection was 514 nM Si, r.s.d. 2.1 %, sampling frequency 40 s/h, reagent consumption 700 μL/sample, and using deionized water as the carrier solution.  more » « less
Award ID(s):
1924690
PAR ID:
10535450
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
ELSEVIER
Date Published:
Journal Name:
Talanta
Volume:
276
ISSN:
0039-9140
Page Range / eLocation ID:
126183
Subject(s) / Keyword(s):
Programmable flow injection Lab-on-valve Silicate Salinity Phosphate interference Autodilution
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Nutrient pollution remains one of the greatest threats to water quality and imposes numerous public health and ecological concerns. Phosphate, the most common form of phosphorus, is one of the key nutrients necessary for plant growth. However, phosphate concentration in water should be carefully monitored for environmental protection requirements. Hence, an easy-to-use, field-deployable, and reliable device is needed to measure phosphate concentrations in the field. In this study, an inexpensive dip strip is developed for the detection of low concentrations of phosphate in water and seawater. In this device, ascorbic acid/antimony reagent was dried on blotting paper, which served as the detection zone, and was followed by a wet chemistry protocol using the molybdenum method. Ammonium molybdate and sulfuric acid were separately stored in liquid form to significantly improve the lifetime of the device and enhance the reproducibility of its performance. The device was tested with deionized water and Sargasso Sea seawater. The limits of detection and quantification for the optimized device using a desktop scanner were 0.134 ppm and 0.472 ppm for phosphate in water and 0.438 ppm and 1.961 ppm in seawater, respectively. The use of the portable infrared lightbox previously developed at our lab improved the limits of detection and quantification by a factor of three and were 0.156 ppm and 0.769 ppm for the Sargasso Sea seawater. The device’s shelf life, storage conditions, and limit of detection are superior to what was previously reported for the paper-based phosphate detection devices. 
    more » « less
  2. Mechanochemistry initiated the reaction of hydrogen-terminated porous silicon (H/por-Si) powder with arginine. Samples were analyzed using Fourier-transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), zeta potential, scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. Arginine, which was physisorbed onto the surface of por-Si, blue-shifted the peak PL intensity from ~630 nm for the H/por-Si to ~565 nm for arginine-coated por-Si. Grinding for 4 h reduced >80% of the initially 2–45 µm particles to <500 nm, but was observed to quench the PL. With appropriate rinsing and centrifugation, particles in the 100 nm range were isolated. Rinsing ground powder with water was required to remove the unreacted arginine. Without rinsing, excess arginine induced the aggregation of passivated particles. However, water reacted with the freshly ground por-Si powder producing H2. A zeta potential of +42 mV was measured for arginine-terminated por-Si particles dispersed in deionized water. This positive value was consistent with termination such that NH2 groups extended away from the surface. Furthermore, this result was confirmed by FTIR spectra, which suggested that arginine was bound to silicon through the formation of a covalent Si–O bond. 
    more » « less
  3. Abstract The Southern Ocean (SO) has been an area of biogeochemical interest due to the presence of macronutrients (N, P, and Si) but lack of the expected primary production response, which is thought to be primarily due to Fe limitation. Because primary production is associated with increased drawdown of atmospheric CO2, it is important to quantify the fluxes of Fe and other nutrients into the SO. Here we present data from subaerial streams that flow into the Ross Sea, a sector of the coastal SO. Water samples were collected in the McMurdo Dry Valleys, Antarctica, and analyzed for macronutrients and Fe to determine the potential impact of terrestrial water input on the biogeochemistry of coastal oceanic waters. The physiochemical forms of Fe were investigated through analysis of three operationally defined forms: acid‐dissolvable Fe (no filtration), filterable Fe (<0.4 μm), and dissolved Fe (<0.2 μm). The combined average flux from two McMurdo Dry Valley streams was approximately 240 moles of filterable Fe per year. The dissolved fraction of Fe made up 18%–27% of the filterable Fe. The stream data yield an average filterable stoichiometry of N3P1Si100Fe0.8, which is substantially different from the planktonic composition and suggests that these streams are a potential source of Fe and P, relative to N and Si, to coastal phytoplankton communities. While the Fe flux from these streams is orders of magnitude less than estimated eolian and iceberg sources, terrestrial streams are expected to become a more significant source of Fe to the Ross Sea in the future. 
    more » « less
  4. Abstract The aim of this study was to develop a high‐performance liquid chromatography–tandem mass spectrometry method for the determination of 6‐cyanodopamine, 6‐nitrodopamine, 6‐nitrodopa, 6‐nitroadrenaline and 6‐bromodopamine in human plasma samples. Strata‐X 33 μm solid‐phase extraction cartridges were used for the extraction of the catecholamines from human plasma samples. The catecholamines were separated in a 150 × 3 mm Shim‐pack GIST C18‐AQ column with 3 μm particle size, placed in an oven at 40°C and perfused with 82% mobile phase A (acetonitrile–H2O; 90:10, v/v) + 0.4% acetic acid and 18% mobile phase B (deionized H2O) + 0.2% formic acid at a flow rate of 340 μl/min in isocratic mode. The injected volume was 4 μl and the run lasted 4 min. The method was linear from 0.1 to 20 ng/ml and the lower limit of quantification was 0.1 ng/ml for all analytes. The method was applied to evaluate the plasma levels of catecholamines in plasma of patients with chronic kidney disease and allowed the detection for the first time of circulating levels of the novel catecholamines 6‐bromodopamine and 6‐cyanodopamine. 
    more » « less
  5. Quantifying trace levels of microplastics in complex environmental media remains a challenge. In this study, an approach combining field collection of samples from different depths, sample size fractionation, and plastic quantification via pyrolysis-gas chromatography–mass spectrometry (Py-GC–MS) was employed to identify and quantify microplastics at two public beaches along the northeast coast of the U.S. (Salisbury beach, MA and Hampton beach, NH). A simple sampling tool was used to collect beach sand from depth intervals of 0–5 cm and 5–10 cm, respectively. The samples were sieved to give three size fractions: coarse (>1.2 mm), intermediate (100 μm–1.2 mm), and fine (1.2 μm–100 μm) particles. Following density separation and wet peroxide oxidation, a low-temperature solvent extraction protocol involving 2-chlorophenol was used to extract polyester (PET), polystyrene (PS), polyamide (PA), and polyvinyl chloride (PVC). The extract was analyzed using Py-GC–MS for the respective polymers, while the solid residue was pyrolyzed separately for polyethylene (PE) and polypropylene (PP). The one-step solvent extraction method significantly simplified the sample matrix and improved the sensitivity of analysis. Among the samples, PET was detected in greater quantities in the fine fraction than in the intermediate size fraction, and PET fine particles were located predominantly in the surface sand. Similar to PET, PS was detected at higher mass concentrations in the fine particles in most samples. These results underscore the importance of beach environment for plastic fragmentation, where a combination of factors including UV irradiation, mechanical abrasion, and water exposure promote plastic breakdown. Surface accumulation of fine plastic particles may also be attributed to transport of microplastics through wind and tides. The proposed sample treatment and analysis methods may allow sensitive and quantitative measurements of size or depth related distribution patterns of microplastics in complex environmental media. 
    more » « less