Geometric characterization of polymeric capillaries.

There are few methods in the literature to measure the inner diameter of very small capillaries. Although silica capillaries are more commonly used, synthetic polymer capillaries are preferred in some applications. The technology for producing them is not as mature. Aside from the absolute value of the inner diameter, the circularity, concentricity (a quantitative index is defined here for the first time) and the bore uniformity of such capillaries are of interest. Beyond microscopy, we describe multiple methods that determine the capillary inner diameter, averaged over a given length. The measurements variously depended on the capillary internal volume, length and cross section, and the resistance to fluid flow. The different approaches produced mutually consistent results. We show that when the internal diameter is not uniform, the different dependence on diameter that two such methods may exhibit, can be exploited to determine the true mean diameter as well as its variance. Finally, for open tubular liquid chromatography, where performance acutely depends on the inner diameter, we surprisingly find that while the mean i.d. may be the dominant determinant of efficiency, bore variance has little to no effect on the performance.

In Silico investigation of a post liquid chromatographic membrane extractor.

Recently, a vapor permeable membrane was coupled to ion exclusion chromatography for the selective removal of volatile fatty acids. The volatile components are isolated from the acidic chromatographic eluent flowing through the lumen of the membrane tube and isolated in the annular portion of a surrounding extractant jacket flow where they are measured conductometrically. The extractor dimensions and extractant flow rate must be balanced to maintain chromatographic efficiency and improve sensitivity. The extraction process has been simulated by a series of repeated transfers between two flowing streams using experimentally measured permeation rates. Five n-alkyl carboxylic acids (formic-pentanoic acid) separated by ion exclusion are used as the test suite for generating and validating the model. The dependence of the peak broadening and concentration factor upon the various parameters, particularly the length, have been reduced to simple empirical formulas which may be used for optimization.

Automated Programmable Preparation of Carbonate-Bicarbonate Eluents for Ion Chromatography with Pressurized Carbon Dioxide.

We introduce a novel carbonate-bicarbonate eluent generation system in which CO2 is introduced using programmable CO2 pressures across a membrane into a flowing solution of electrodialytically generated high purity KOH. Many different gradient types are possible, including situations where gradients are run both on the [KOH] and the CO2 pressure. The system is more versatile than current electrodialytic carbonate eluent generators and can easily generate significantly higher eluent concentrations (at least to 40 mM carbonate), paving the way for future higher capacity columns. Demonstrably purer carbonate-bicarbonate eluent systems are possible compared to manually prepared carbonate-bicarbonate eluents and with considerable savings in time. Performance in different modes is examined. The dissolved CO2 is removed by a carbon dioxide removal device prior to detection. Best case noise levels are within a factor of 2-3 of best case suppressed hydroxide eluent operation. The eluent system allows particular latitude in controlling elution order/time of polyprotic acid analytes. Although CO2 introduction is possible prior to hydroxide eluent generation, this configuration causes complications because of electroreduction of CO2 to formate.

Automated programmable pressurized carbonic acid eluent ion exclusion chromatography of organic acids.

Conductometric ion exclusion chromatography of weak acids does not enjoy the same degree of success as its counterpart in suppressed conductometric anion exchange chromatography. Compared to the latter, eluent preparation is not automated. Commonly, a strong acid is used as the eluent leading to a relatively high-detector background and poorer limits of detection. In addition, generally applicable gradient elution has not been possible. We introduce the automated preparation of carbonic acid eluents at concentrations exceeding 0.15M by introducing CO2 into a flowing water stream through the walls of a Teflon AF® capillary tube under pressure; the resulting eluent concentration is controlled by varying the CO2 pressure in a programmed manner. The acidic carbonic acid solution functions as the eluent and can be almost completely removed (detector background 1.2-1.6µS/cm) by an improved carbon dioxide removal device before detection. Theoretical and practical considerations are discussed and illustrative isocratic and gradient ion exclusion chromatography is demonstrated.

Evaluation of Amount of Blood in Dry Blood Spots: Ring-Disk Electrode Conductometry.

A fixed area punch in dried blood spot (DBS) analysis is assumed to contain a fixed amount of blood, but the amount actually depends on a number of factors. The presently preferred approach is to normalize the measurement with respect to the sodium level, measured by atomic spectrometry. Instead of sodium levels, we propose electrical conductivity of the extract as an equivalent nondestructive measure. A dip-type small diameter ring-disk electrode (RDE) is ideal for very small volumes. However, the conductance (G) measured by an RDE depends on the depth (D) of the liquid below the probe. There is no established way of computing the specific conductance (σ) of the solution from G. Using a COMSOL Multiphysics model, we were able to obtain excellent agreement between the measured and the model predicted conductance as a function of D. Using simulations over a large range of dimensions, we provide a spreadsheet-based calculator where the RDE dimensions are the input parameters and the procedure determines the 99% of the infinite depth conductance (G99) and the depth D99 at which this is reached. For typical small diameter probes (outer electrode diameter ∼ <2 mm), D99 is small enough for dip-type measurements in extract volumes of ∼100 µL. We demonstrate the use of such probes with DBS extracts. In a small group of 12 volunteers (age 20-66), the specific conductance of 100 µL aqueous extracts of 2 µL of spotted blood showed a variance of 17.9%. For a given subject, methanol extracts of DBS spots nominally containing 8 and 4 µL of blood differed by a factor of 1.8-1.9 in the chromatographically determined values of sulfate and chloride (a minor and major constituent, respectively). The values normalized with respect to the conductance of the extracts differed by ∼1%. For serum associated analytes, normalization of the analyte value by the extract conductance can thus greatly reduce errors from variations in the spotted blood volume/unit area.

Water ICE: Ion Exclusion Chromatography of Very Weak Acids with a Pure Water Eluent.

Separation of ions or ionizable compounds with pure water as eluent and detecting them in a simple fashion has been an elusive goal. It has been known for some time that carbonic acid can be separated from strong acids by ion chromatography in the exclusion mode (ICE) using only water as the eluent. The practice of water ICE was shown feasible for very weak acids like silicate and borate with a dedicated element specific detector like an inductively coupled plasma mass spectrometer (ICPMS), but this is rarely practical in most laboratories. Direct conductometric detection is possible for H2CO3 but because of its weak nature, not especially sensitive; complex multistep ion exchange methods do not markedly improve this LOD. It will clearly be impractical in acids that are weaker still. By using a permeative amine introduction device (PAID, Anal. Chem. 2016 , 88 , 2198 - 2204 ) as a conductometric developing agent, we demonstrate that a variety of weak acids (silicate, borate, arsenite, cyanide, carbonate, and sulfide) cannot only be separated on an ion exclusion column, they can be sensitively detected (LODs 0.2-0.4 µM). We observe that the elution order is essentially the same as that on a nonfunctionalized poly(styrene-divinylbenzene) column using 1-10% acetonitrile as eluent and follows the reverse order of the polar surface area (PSA) of the analyte molecules. PSA values have been widely used to predict biological transport of pharmaceuticals across a membrane but never to predict chromatographic behavior. We demonstrate the application of the technique by measuring the silicate and borate depth profiles in the Pacific Ocean; the silicate results show an excellent match with results from a reference laboratory.

Temporal variation in groundwater quality in the Permian Basin of Texas, a region of increasing unconventional oil and gas development.

The recent expansion of natural gas and oil extraction using unconventional oil and gas development (UD) practices such as horizontal drilling and hydraulic fracturing has raised questions about the potential for environmental impacts. Prior research has focused on evaluations of air and water quality in particular regions without explicitly considering temporal variation; thus, little is known about the potential effects of UD activity on the environment over longer periods of time. Here, we present an assessment of private well water quality in an area of increasing UD activity over a period of 13months. We analyzed samples from 42 private water wells located in three contiguous counties on the Eastern Shelf of the Permian Basin in Texas. This area has experienced a rise in UD activity in the last few years, and we analyzed samples in four separate time points to assess variation in groundwater quality over time as UD activities increased. We monitored general water quality parameters as well as several compounds used in UD activities. We found that some constituents remained stable over time, but others experienced significant variation over the period of study. Notable findings include significant changes in total organic carbon and pH along with ephemeral detections of ethanol, bromide, and dichloromethane after the initial sampling phase. These data provide insight into the potentially transient nature of compounds associated with groundwater contamination in areas experiencing UD activity.

Conductometric Gradient Ion Exclusion Chromatography for Volatile Fatty Acids.

We describe a fatty acid vapor extractor (FAVE) as a postcolumn device for sensitive detection following ion exclusion chromatographic (ICE) separation of weak acids. The device consists of a single length of a permselective membrane tube surrounded by a jacket that consists of two isolated sections. The separation column effluent flows through the lumen. A suitable strong acid is put in the upstream, short section of the jacket and permeates in, rendering the lumenal flow strongly acidic (pH ≤ 2) that suppresses eluite weak acid dissociation. A lipophilic polysiloxane membrane is selectively permeable to volatile fatty acids (VFAs). A small fraction of the VFAs transfer to a cocurrent receptor stream of water (or a weak base, e.g., dilute hydroxylamine), flowing through the second, longer section of the jacket. Even though the transferred amount of VFAs may be very small (0.5-5%), significantly better detection limits than conventional suppressed conductometric ICE (SCICE) is possible because of the low and stable background (noise <1 nS/cm). It also permits gradient elution, not possible in SCICE. The polysiloxane based FAVE device is highly selective for VFAs, it shows no response to dicarboxylic acids, hydroxycarboxylic acids, or aromatic acids. As such, trace detection of VFAs in the FAVE extractant is possible while other components can still be monitored conventionally in the FAVE lumenal effluent. Various parameters, related both to device design and operation were studied. The FAVE provides isolation from the eluent matrix and can be used for other detectors where the eluent matrix is incompatible with the detector.

Simultaneous Electrodialytic Preconcentration and Speciation of Chromium(III) and Chromium(VI).

Large amounts of chromium (Cr) compounds are used for manufacturing of various products and various chemical processes. Some inevitably find their way into the environment. Environmental Cr is dominantly inorganic and is either in the cationic +3 oxidation state or in the anionic oxochromium +6 oxidation state. The two differ dramatically in their implications; Cr(III) is essential to human nutrition and even sold as a supplement, while Cr(VI) is a potent carcinogen. Drinking water standards for chromium may be based on total Cr or Cr(VI) only. Thus, Cr speciation analysis is very important. Despite their high sensitivity, atomic spectrometric techniques or induction coupled plasma-mass spectrometry (ICP-MS) cannot directly differentiate the oxidation states. We present here a new electrodialytic separation concept. Sample analyte ions are quantitatively transferred via appropriately ionically functionalized dialysis membranes into individual receptors that are introduced into the ICP-MS. There was no significant conversion of Cr(VI) to Cr(III) or vice versa during the very short (6 s) separation process. Effects of salinity (up to ∼20 mM NaCl) can be eliminated with proper membrane functionalization and receptor optimization. With the ICP-MS detector we used, the limits of detection for either form of Cr was 0.1 µg/L without preconcentration. Up to 10-fold preconcentration was readily possible by increasing the donor solution flow rate relative to the acceptor solution flow rates. The proposed approach permits simultaneous matrix isolation, preconcentration, and chromium speciation.

A Comprehensive Analysis of Groundwater Quality in The Barnett Shale Region.

The exploration of unconventional shale energy reserves and the extensive use of hydraulic fracturing during well stimulation have raised concerns about the potential effects of unconventional oil and gas extraction (UOG) on the environment. Most accounts of groundwater contamination have focused primarily on the compositional analysis of dissolved gases to address whether UOG activities have had deleterious effects on overlying aquifers. Here, we present an analysis of 550 groundwater samples collected from private and public supply water wells drawing from aquifers overlying the Barnett shale formation of Texas. We detected multiple volatile organic carbon compounds throughout the region, including various alcohols, the BTEX family of compounds, and several chlorinated compounds. These data do not necessarily identify UOG activities as the source of contamination; however, they do provide a strong impetus for further monitoring and analysis of groundwater quality in this region as many of the compounds we detected are known to be associated with UOG techniques.

Enigmatic ion-exchange behavior of myo-inositol phosphates.

The separation of myo-inositol mono-, di-, tri-, tetra-, pentakis-, and hexakisphosphate (InsP1, InsP2, InsP3, InsP4, InsP5, InsP6) was carried out using hydroxide eluent ion chromatography. Acid hydrolysis of InsP6 (phytate) was used to prepare a distribution of InsPs, ranging from InsP1 to InsP5's and including unhydrolyzed InsP6. Counting all possible positional isomers (many of which have stereoisomers that will not be separable by conventional ion exchange), 40 chromatographically separable peaks are possible; up to 22 were separated and identified by mass spectrometry. InsPs show unusual ion-exchange behavior in two respects: (a) the retention order is not monotonically related with the charge on the ion and (b) at the same hydroxide eluent concentration, retention is greatly dependent on the eluent metal cation. The retention of InsP3-InsP6 was determined to be controlled by steric factors while elution was influenced by eluent cation complexation. These highly phosphorylated InsPs have a much greater affinity for alkali metals (Li(+) > Na(+) > K(+)) than quaternary ammonium ions. This difference in cation affinity was exploited to improve separation through the use of a tetramethylammonium hydroxide-sodium hydroxide gradient.

Nonlinear absorbance amplification using a diffuse reflectance cell: total organic carbon monitoring at 214 nm.

We present an absorption spectrometric method using a polytetrafluoroethylene (PTFE) cell as a diffuse reflector. The system was used for monitoring ultrapure water. All compounds absorb to some degree at low UV wavelengths, and the absorption at 214 nm from a zinc lamp source was monitored using a charge-coupled device (CCD) spectrometer. The absorption was interpreted in terms of total organic carbon present. The cell acts as a nonlinear absorbance amplifier, improving both the limit of detection (LOD) and the dynamic range. Potassium hydrogen phthalate (KHP) and glucose were used to evaluate the system and provided respective LODs of 46.5 ng/L and 4.5 mg/L as carbon. Although the physical path length was 25 cm, a maximum effective path length of 280 cm was observed at the lowest tested KHP concentrations. The system is intended for real-time monitoring of ultrapure water.

What can in situ ion chromatography offer for Mars exploration?

The successes of the Mars exploration program have led to our unprecedented knowledge of the geological, mineralogical, and elemental composition of the martian surface. To date, however, only one mission, the Phoenix lander, has specifically set out to determine the soluble chemistry of the martian surface. The surprising results, including the detection of perchlorate, demonstrated both the importance of performing soluble ion measurements and the need for improved instrumentation to unambiguously identify all the species present. Ion chromatography (IC) is the state-of-the-art technique for soluble ion analysis on Earth and would therefore be the ideal instrument to send to Mars. A flight IC system must necessarily be small, lightweight, low-power, and have low eluent consumption. We demonstrate here a breadboard system that addresses these issues by using capillary IC at low flow rates with an optimized eluent generator and suppressor. A mix of 12 ions known or plausible for the martian soil, including 4 (oxy)chlorine species, has been separated at flow rates ranging from 1 to 10 µL/min, requiring as little as 200 psi at 1.0 µL/min. This allowed the use of pneumatic displacement pumping from a pressurized aluminum eluent reservoir and the elimination of the high-pressure pump entirely (the single heaviest and most energy-intensive component). All ions could be separated and detected effectively from 0.5 to 100 µM, even when millimolar concentrations of perchlorate were present in the same mixtures.

Anion composition of açaí extracts.

Many products labeled açaí are presently marketed as natural supplements with various claimed health benefits. Authentic açaí is expensive; as a result, numerous products labeled as containing açaí are being sold that actually contain little or no açaí. Authentic açaí samples from Brazil and Florida as well as several reputed açaí products were analyzed by suppressed conductometric anion chromatography. Columns with different selectivities were used to obtain a complete separation of all anions. Tandem mass spectrometry was used for confirmation of the less common ions. Quinate, lactate, acetate, formate, galacturonate, chloride, sulfate, malate, oxalate, phosphate, citrate, isocitrate, and myo-inositol hexakisphosphate (phytate) were found. Only the Florida açaí had detectable levels of hexanoate. No açaí sample had any detectable levels of tartrate, which is present in abundance in grape juice, the most common adulterant. The highly characteristic anion profile and in particular the absence of tartrate can readily be used to identify authentic açaí products. Açaí from Florida had a 6 times greater level of phytate. The present analytical approach for phytate may be superior to extant methods.

Breastfed infants metabolize perchlorate.

Bifidobacteria are the dominant intestinal bacteria in breastfed infants. It is known that they can reduce nitrate. Although no direct experiments have been conducted until now, inferred pathways for Bifidobacterium bifidum include perchlorate reduction via perchlorate reductase. We show that when commercially available strains of bifidobacteria are cultured in milk, spiked with perchlorate, perchlorate is consumed. We studied 13 breastfed infant-mother pairs who provided 43 milk samples and 39 infant urine samples, and 5 formula-fed infant-mother pairs who provided 21 formula samples and 21 infant urine samples. Using iodine as a conservative tracer, we determined the average urinary iodine (UI) to milk iodine (MI) concentration ratio to be 2.87 for the breastfed infants. For the same samples, the corresponding perchlorate concentration ratio was 1.37 (difference significant, p < 0.001), indicating that perchlorate is lost. For the formula fed infant group the same ratios were 1.20 and 1.58; the difference was not significant (p = 0.68). However, the small number of subjects in the latter group makes it more difficult to conclude definitively whether perchlorate reduction does or does not occur.

Fenton digestion of milk for iodinalysis.

Iodine is an essential micronutrient especially important in the neurodevelopment of infants. Spot samples of urinary iodine (UI) are used as an epidemiologic index of adult iodine nutrition. Individual infant iodine nutrition is of vital importance, but infant urine is difficult to collect, much less a 24 h sample. Monitoring the intake provides a pragmatic solution for determining infant iodine nutrition. Because of the high solids content of milk and the possible existence of iodine in an organically bound form, sample digestion is obligatory. The U.S. Food and Drug Administration, for example, uses wet ashing by HClO(4); special precautions and fume hoods are required. We present a method of Fenton digestion of human and bovine milk samples and infant formula. No specialized equipment or hazardous reagents are used; measurement is made by isotope dilution inductively coupled plasma mass spectrometry. In Fenton digestion, Fe(II) and H(2)O(2) oxidizes the sample. In an interlaboratory study, excellent agreement (r(2) = 0.9934) was observed with results obtained by HClO(4) digestion and Sandel-Kolthoff kinetic colorimetry. Average recoveries of iodide, triiodothyronine, and thyroxine ranged between 100% and 101%. Following digestion, iodine was found to exist entirely as iodide. Control of pH is imperative if loss cannot be corrected for by isotope dilution. Loss was below 20% for all samples when the pH was between 2.25 and 2.5.

Review of analytical methods for the quantification of iodine in complex matrices.

Iodine is an essential element of human nutrition. Nearly a third of the global population has insufficient iodine intake and is at risk of developing Iodine Deficiency Disorders (IDD). Most countries have iodine supplementation and monitoring programs. Urinary iodide (UI) is the biomarker used for epidemiological studies; only a few methods are currently used routinely for analysis. These methods either require expensive instrumentation with qualified personnel (inductively coupled plasma-mass spectrometry, instrumental nuclear activation analysis) or oxidative sample digestion to remove potential interferences prior to analysis by a kinetic colorimetric method originally introduced by Sandell and Kolthoff ~75 years ago. The Sandell-Kolthoff (S-K) method is based on the catalytic effect of iodide on the reaction between Ce(4+) and As(3+). No available technique fully fits the needs of developing countries; research into inexpensive reliable methods and instrumentation are needed. There have been multiple reviews of methods used for epidemiological studies and specific techniques. However, a general review of iodine determination on a wide-ranging set of complex matrices is not available. While this review is not comprehensive, we cover the principal developments since the original development of the S-K method.