Application of a portable ion chromatograph for real-time field analysis of nitrite and nitrate in soils and soil pore waters.

Real-time monitoring of nitrite and nitrate is crucial for maintaining soil health and promoting plant growth. In this study, a portable ion-chromatograph (IC, Aquamonitrix) analyser, coupled with a field-applicable ultrasonic-assisted extraction method, was utilised for in-field determination of nitrate and nitrite in soils. This is the first application of this type of analyser to soil nutrients. On-site analysis of soil from a local sports field showed 94.8 ± 4.3 µg g-1 nitrate, with LODs of 32.0 µg g-1 for nitrate and 5.4 µg g-1 for nitrite. The results were in close agreement with those obtained using a conventional lab-based IC. Relative standard deviations (%RSDs) for soil analysis using Aquamonitrix were consistently below 10%. The obtained average recoveries of samples spiked with nitrite were 100% and 104% for the portable IC and conventional IC, respectively. Furthermore, to assess the suitability of portable IC for samples with high organic matter content, various natural organic fertilisers were extracted and analysed. The results showed 16.2 ± 0.7 µg g-1 nitrite and 28.5 ± 5.6 µg g-1 nitrate in sheep manure samples with LODs of 2.0 µg g-1 for nitrite and 12.0 µg g-1 for nitrate. The portable IC system was further demonstrated via real-time on-site analysis of soil pore-water acquired using a portable battery-based ceramic pore-water sampler. A continuous increase in nitrate concentration over time was observed (from 80 to 148 µg mL-1) in the soil pore-water in a vegetable garden four days after heavy rain. Unlike conventionally sampled natural waters, 7-day storage of the studied pore water samples revealed no changes in nitrate concentrations. An average of 558 ± 51 µg mL-1 nitrate was detected in the soil pore-water samples analysed on a spinach farm, immediately after irrigation.

Portable IC system enabled with dual LED-based absorbance detectors and 3D-printed post-column heated micro-reactor for the simultaneous determination of ammonium, nitrite and nitrate.

BACKGROUND: The on-site and simultaneous determination of anionic nitrite (NO2-) and nitrate (NO3-), and cationic ammonium (NH4+), in industrial and natural waters, presents a significant analytical challenge. Toward this end, herein a 3D-printed micro-reactor with an integrated heater chip was designed and optimised for the post-column colorimetric detection of NH4+ using a modified Berthelot reaction. The system was integrated within a portable and field deployable ion chromatograph (Aquamonitrix) designed to separate and detect NO2- and NO3-, but here enabled with dual LED-based absorbance detectors, with the aim to provide the first system capable of simultaneous determination of both anions and NH4+ in industrial and natural waters. RESULTS: Incorporating a 0.750 mm I.D. 3D-printed serpentine-based microchannel for sample-reagent mixing and heating, the resultant micro-reactor had a total reactor channel length of 1.26 m, which provided for a reaction time of 1.42 min based upon a total flow rate of 0.27 mL min-1, within a 40 mm2 printed area. The colorimetric reaction was performed within the micro-reactor, which was then coupled to a dedicated 660 nm LED-based absorbance detector. By rapidly delivering a reactor temperature of 70 °C in just 40 s, the optimal conditions to improve reaction kinetics were achieved to provide for limits of detection of 0.1 mg L-1 for NH4+, based upon an injection volume of just 10 µL. Linearity for NH4+ was observed over the range 0-50 mg L-1, n = 3, R2 = 0.9987. The reactor was found to deliver excellent reproducibility when included as a post-column reactor within the Aquamonitrix analyser, with an overall relative standard deviation below 1.2 % for peak height and 0.3 % for peak residence time, based upon 6 repeat injections. SIGNIFICANCE: The printed post-column reactor assembly was integrated into a commercial portable ion chromatograph developed for the separation and detection of NO2- and NO3-, thus providing a fully automated system for the remote and simultaneous analysis of NO2-, NO3-, and NH4+ in natural and industrial waters. The fully automated system was deployed externally within a greenhouse facility to demonstrate this capability.

Simultaneous separation and detection of monochloramine, nitrite, and nitrate by step-gradient mixed-mode ion chromatography: Translation from benchtop to portable ion chromatograph.

BACKGROUND: Nitrite (NO2-) and nitrate (NO3-) can be produced in the distribution systems of chloraminated drinking water due to the nitrification of ammonia. The most applied inorganic chloramine for this purpose, namely monochloramine (NH2Cl), is also released into aquatic environments from water treatment plants' effluent and within industrial waste streams. Within the treatment process, the continuous monitoring of disinfectant levels is necessary to limit the harmful disinfectant by-product (DBP) formation. Currently, NH2Cl can interfere with nutrient analysis in water samples, and there are no analytical techniques available for the simultaneous analysis of NH2Cl, NO2-, and NO3-. RESULTS: A green analytical method based on mixed-mode ion chromatography, specifically ion exchange and ion exclusion modes, was developed for the simultaneous separation and detection of NH2Cl, NO2-, and NO3-. The separation was achieved using a Dionex IonPac AG15 column guard column and a step gradient elution involving deionized water and 120.0 mM NaCl. The method was developed using a benchtop HPLC with a custom-made multi-wavelength UV absorbance detector with a 50-mm flow cell to enable the sensitive detection of NH2Cl, NO2-, and NO3- at 240 nm, 220 nm, and 215 nm, respectively. The developed method was then transferred to a portable ion chromatography (IC) system, the Aquamonitrix analyser. The total run time was less than 10 min for both systems. The benchtop HPLC method had a limit of detection (LOD) of 0.07 µg mL-1 as Cl2 for NH2Cl, 0.01 µg mL-1 for NO2-, and 0.03 µg mL-1 for NO3-. The LODs obtained using the portable Aquamonitrix analyser were found to be 0.36 µg mL-1 as Cl2, 0.02 µg mL-1, and 0.11 µg mL-1 for NH2Cl, NO2-, and NO3-, respectively. Excellent linearity (r ≥ 0.9999) was achieved using the portable analyser over the studied concentration ranges. The developed system was applied to the analysis of spiked municipal drinking water samples and showed excellent repeatability for the three analytes at three different concentration levels (RSD of triplicate recovery experiments ≤ 1.9 %). Moreover, the variation in retention time was negligible for the three target analytes with RSD ≤ 0.8 % over 12 runs. SIGNIFICANCE: We are reporting the first ion chromatographic method for the simultaneous separation and detection of NH2Cl, NO2-, and NO3- in water samples. The monitoring of NH2Cl, NO2-, and NO3- is critical for the determination of disinfectant dosing, water quality, and nitrification status. The developed method can be applied using a benchtop HPLC or via the portable automated IC system to monitor for the three target compounds analysis in water treatment plants.

Ion chromatograph with three-dimensional printed absorbance detector for indirect ultraviolet absorbance detection of phosphate in effluent and natural waters.

An ion chromatography system employing a low-cost three-dimensional printed absorbance detector for indirect ultraviolet detection towards portable phosphate analysis of environmental and industrial waters has been developed. The optical detection cell was fabricated using stereolithography three-dimensional printing of nanocomposite material. Chromatographic analysis and detection of phosphate were carried out using a CS5A 4 × 250 mm analytical column with indirect ultraviolet detection using a 255 nm light-emitting diode. Isocratic elution using a 0.6 mM potassium phthalate eluent combined with 1.44 mM sodium bicarbonate was employed at a flow rate of 0.75 mL/min. A linear calibration range of 0.5 to 30 mg/L PO4 3- applicable to environmental and wastewater analysis was achieved. For retention time and peak area repeatability, relative standard deviation values were 0.68 and 4.09%, respectively. Environmental and wastewater samples were analyzed with the optimized ion chromatography platform and the results were compared to values obtained by an accredited ion chromatograph. For the analysis of environmental samples, relative errors of <14 % were achieved. Recovery analysis was also carried out on both freshwater and wastewater samples and recovery results were within the acceptable range for water analysis using standard ion chromatography methods.

Portable analyser using two-dimensional ion chromatography with ultra-violet light-emitting diode-based absorbance detection for nitrate monitoring within both saline and freshwaters.

A portable and automated IC system with a dual-capability for the analysis of both fresh and saline environmental waters has been developed. Detection of nitrate in complex matrices such as seawater was achieved by the employment of an automated two-dimensional (heart-cut) IC method utilised in tandem with on-column matrix elimination, using a sodium chloride eluent. The system also demonstrated the capability to switch to a second mode of analysis, whereby direct one-dimensional IC analysis was employed to rapidly detect nitrite and nitrate in freshwater, with direct UV LED based absorption detection in under 3 minutes. Calibration curves using a 195 µL sample loop were generated for both freshwater and artificial seawater samples. For marine analysis, an analytical range of 0.1 mg L-1 - 40 mg L-1 NO3- was possible, while an analytical range (0.1 mg L-1 - 15 mg L-1 NO2-, 0.2 - 30 mg L-1 NO3-) appropriate for freshwater analysis was also achieved. Chromatographic repeatability for both marine and freshwater analysis was verified over 40 sequential runs with RSD values of < 1% demonstrated for both peak area and retention times for each mode of analysis. The selectivity of both methods was demonstrated with interference tests with common anions present in environmental waters. Recovery analysis was carried out on marine samples from Tramore Bay, Co. Waterford, Ireland, and the systems analytical performance was compared with that of an accredited IC following environmental sample analysis.

Peptide Chitosan/Dextran Core/Shell Vascularized 3D Constructs for Wound Healing.

Three-dimensional (3D) bioprinting has emerged to create novel cell-based therapies for regenerative medicine applications. Vascularized networks within engineered constructs are required, and toward this end, we report a promising strategy using core-shell (c/s) extrusion 3D-bioprinting technology that employs biomimetic biomaterials to construct regenerative, prevascularized scaffolds for wound care. A custom-designed cell-responsive bioink consisting of a 13% (w/v) cell-laden gelatin methacryloyl (GelMA) shell surrounding a peptide-functionalized, succinylated chitosan (C)/dextran aldehyde (D) cell-laden core was successfully bioprinted resulting in organized microdesigns exhibiting excellent cell viability and subsequent vessel formation. Our templating strategy takes advantage of GelMA's intrinsic thermoreversible properties of low degree of acryloyl functionalization used in combination with a lightly, chemically cross-linked peptide-CD core to serve as temporal structural supports that stabilize during extrusion onto a cooled platform. Mechanical integrity was further strengthened layer-by-layer via GelMA UV photo-cross-linking. We report the first example of GelMA used in combination with a peptide-CD bioink to c/s 3D-bioprint regenerative, prevascularized constructs for wound care. Particular cell adhesion and proteolytic peptide-CD functionalized pair combinations, P15/MMP-2 and P15/cRGD, were found to significantly increase growth of human bone-marrow-derived mesenchymal stems cells (hBMSCs) and human umbilical vein endothelial cells (HUVECs). The constructs delivered two cell types: hBMSCs in the shell bioink and HUVECs within the core bioink. Cord-like, natural microvascularization was shown with endothelial cell marker expression as confirmed by immunofluorescence (IF) staining exhibiting tubelike structures. In addition, in vitro skin wound healing activity of the construct showed a ∼twofold rate of wound closure. Overall, c/s 3D-bioprinted, peptide-CD/GelMA constructs provided the appropriate microenvironment for in vitro stem and endothelial cell viability, delivery, and differentiation. We foresee these custom constructs as representing a fundamental step toward engineering larger scale regenerative, prevascularized tissues.

Fully automated, low-cost ion chromatography system for in-situ analysis of nitrite and nitrate in natural waters.

A cost-effective, automated and portable IC has been developed for in-situ analysis of nitrite and nitrate in natural waters. The system employed 3D printed pumps for eluent delivery and a deep-UV LED based optical detector. Isocratic separation and selective detection of nitrite and nitrate was achieved in under 3 min. The total weight of the analyser was ~11 kg, and included electronics along with a sample intake system for automated analysis. Linear calibration ranges were generated using different sample injection loops. Using a 150 µL loop, an analytical range (0.05-30 mg L-1 NO2-, 0.10-75 mg L-1 NO3-) suitable for freshwater analysis was generated, while using a 10 µL loop an analytical range (0.30-100 mg L-1 NO2-, 2.5-500 mg L-1 NO3-) suitable for effluent and domestic wastewater analysis was achieved. Chromatographic repeatability demonstrated by the system is graphically presented and RSD values of <4% were obtained in terms of peak area and retention time over 82 sequential runs. The system was deployed in-situ at multiple sites for varying deployment periods analysing septic tank water, effluent from a waste water treatment plant and stream water. The data generated by the in-situ system were comparable to grab sample data generated by accredited laboratory instrumentation.

Integrated 3D printed heaters for microfluidic applications: Ammonium analysis within environmental water.

A multi-material 3D printed microfluidic reactor with integrated heating is presented, which was applied within a manifold for the colorimetric determination of ammonium in natural waters. Graphene doped polymer was used to provide localised heating when connected to a power source, achieving temperatures of up to 120 °C at 12 V, 0.7 A. An electrically insulating layer of acrylonitrile butadiene styrene (ABS) polymer or a new microdiamond-ABS polymer composite was used as a heater coating. The microdiamond polymer composite provided higher thermal conductivity and uniform heating of the serpentine microreactor which resulted in greater temperature control and accuracy in comparison to pure ABS polymer. The developed heater was then applied and demonstrated using a modified Berthelot reaction for ammonium analysis, in which the microreactor was configured at a predetermined optimised temperature. A 5-fold increase in reaction speed was observed compared to previously reported reaction rates. A simple flow injection analysis set up, comprising the microfluidic heater along with an LED-photodiode based optical detector, was assembled for ammonium analysis. Two river water samples and two blind ammonium standards were analysed and estimated concentrations were compared to concentrations determined using benchtop IC. The highest relative error observed following the analysis of the environmental samples was 11% and for the blind standards was 5%.

Physical Characteristics of Elite Youth Female Soccer Players Characterized by Maturity Status.

Emmonds, S, Scantlebury, S, Murray, E, Turner, L, Robsinon, C, and Jones, B. Physical characteristics of elite youth female soccer players characterized by maturity status. J Strength Cond Res 34(8): 2321-2328, 2020-The purpose of this study was to investigate the influence of maturity status on the physical characteristics of youth female soccer players. One hundred fifty-seven players from 3 elite soccer academies in England completed assessments of anthropometry, strength (isometric midthigh pull), lower-body power (countermovement jump [CMJ]), aerobic capacity (Yo-Yo intermittent recovery test level 1), change of direction (CoD: 505-left/right), and speed (10 and 30 m). Each player was classified into 1 of 6 maturity groups based on their estimated years from peak height velocity (YPHV). Magnitude-based inferences were used to assess for the practical significance between consecutive groups. Speed, CoD time, CMJ, and aerobic capacity were all possibly most likely better in more mature players. However, there was a likely difference in relative peak force between maturity groups -0.5 YPHV (27.13 ± 4.24 N·Kg) and 0.5 YPHV (24.62 ± 3.70 N·Kg), which was associated with a likely difference in 10-m sprint time (-0.5 YPHV: 2.00 ± 0.12 vs. 0.5 YPHV 2.08 ± 0.16 seconds) and unclear changes in CMJ and CoD time. Findings provide novel comparative data for this cohort relative to maturity status and can be used by strength and conditioning coaches to inform the design of training programs for youth female soccer players. Strength and conditioning coaches should be aware that youth female soccer players may experience a decrease in relative strength around peak height velocity, which may impact upon the speed, CoD time, and CMJ of players.

Low cost 235 nm ultra-violet light-emitting diode-based absorbance detector for application in a portable ion chromatography system for nitrite and nitrate monitoring.

A low cost, UV absorbance detector incorporating a 235 nm light emitting diode (LED) for portable ion chromatography has been designed and fabricated to achieve rapid, selective detection of nitrite and nitrate in natural waters. The optical cell was fabricated through micromilling and solvent vapour bonding of two layers of poly (methyl methacrylate) (PMMA). The cell was fitted within a 3D printed housing and the LED and photodiode were aligned using 3D printed holders. Isocratic separation and selective detection of nitrite and nitrate was achieved in under 2.5 min using the 235 nm LED based detector and custom electronics. The design of the new detector assembly allowed for effective and sustained operation of the deep UV LED source at a low current (<10 mA), maintaining consistent and low LED temperatures during operation, eliminating the need for a heat sink. The detector cell was produced at a fraction of the cost of commercial optical cells and demonstrated very low stray light (0.01%). For retention time and peak area repeatability, RSD values ranged from 0.75 to 1.10 % and 3.06-4.19 %, respectively. Broad dynamic linear ranges were obtained for nitrite and nitrate, with limits of detection at ppb levels. The analytical performance of the IC set up with optical cell was compared to that of an ISO-accredited IC through the analysis of five various water samples. Relative errors not exceeding 6.86% were obtained for all samples. The detector was also coupled to a low pressure, low cost syringe pump to assess the potential for use within a portable analytical system. RSD values for retention time and peak area using this simple configuration were <1.15% and <3.57% respectively, highlighting repeatability values comparable to those in which a commercial HPLC pump was used.

Emergency Departments as the Health Safety Nets of Society: A Descriptive and Multicenter Analysis of Social Worker Support in the Emergency Room.

Introduction Social Work (SW) referrals made in the emergency department (ED) highlight the weaknesses in the existing support system for vulnerable and disadvantaged patients. SW personnel play a pivotal role in some EDs but are not integrated into the team in several jurisdictions. Our objective was to provide a detailed description of the need for SW support in the ED setting by describing SW consultation patterns in an urban ED location. Methods A three-year analysis of ED SW referrals made through a network of four acute care hospitals serving a city population of 1.2 million inhabitants where social workers operate from 8 a.m. to 10 p.m. The study design was descriptive reporting proportions. The descriptors of interest were the types of ED patients receiving SW consultations and the reasons for patient referral to the SW Department. Results During the study period, there were 46,970 SW consultations, representing 8.02% of the 572,804 patients who visited the ED across Calgary, yielding 42.9 referrals per day to social workers through the ED. Consultations for domestic violence were three times more prevalent for women (6% of referrals). However, domestic violence consultations were still an active issue for men (1.9%). Comparisons by age group yielded illness adjustments (15.3%), discharge planning (31.2%), and legal decision making (23.9%) as the most common reasons for referral of patients over 75 years old; 92.8% of patients over 75 years were admitted following the SW consultation. Reasons for deferral of patients under 30 years of age were illness adjustments (12.2%), discharge planning (16.4 %), and legal decision making (1.4%); 57.3% of patients under 30 years were admitted following the consultation. Addiction/drug use and homelessness were more common in those under the age of 30, comprising 24.1% and 15.4% of the SW referrals, respectively, compared to 1.6% and 0.4% of referrals for those over age 75, respectively. Conclusions The demand for SW support is significant and complex in these large urban EDs. However, the impact on patient care and resource use is substantial, and the data indicates that SW integration may be of universal benefit to EDs. Further studies are warranted to accurately characterize the amount and type of SW necessary for optimal patient outcomes and hospital resource use.

Miniaturized capillary ion chromatograph with UV light-emitting diode based indirect absorbance detection for anion analysis in potable and environmental waters.

A miniaturized, flexible, and low-cost capillary ion chromatography system has been developed for anion analysis in water. The ion chromatography has an open platform, modular design, and allows for ease of modification. The assembled platform weighs ca. 0.6 kg and is 25 × 25 cm in size. Isocratic separation of common anions (F- , Cl- , NO2- , Br- , and NO3- ) could be achieved in under 15 min using sodium benzoate eluent at a flow rate of 3 µL/min, a packed capillary column (0.150 × 150 mm) containing Waters IC-Pak 10 µm anion exchange resin, and light-emitting diode based indirect UV detection. Several low UV light-emitting diodes were assessed in terms of sensitivity, including a new 235 nm light-emitting diode, however, the highest sensitivity was demonstrated using a 255 nm light-emitting diode. Linear calibration ranges applicable to typical natural water analysis were obtained. For retention time and peak area repeatability, relative standard deviation values ranged from 0.60-0.95 and 1.95-3.53%, respectively. Several water samples were analysed and accuracy (recovery) was demonstrated through analysis of a prepared mixed anion standard. Relative errors of -0.36, -1.25, -0.80, and -0.76% were obtained for fluoride, chloride, nitrite, and nitrate, respectively.

Cavity-enhanced coherent light scattering from a quantum dot.

The generation of coherent and indistinguishable single photons is a critical step for photonic quantum technologies in information processing and metrology. A promising system is the resonant optical excitation of solid-state emitters embedded in wavelength-scale three-dimensional cavities. However, the challenge here is to reject the unwanted excitation to a level below the quantum signal. We demonstrate this using coherent photon scattering from a quantum dot in a micropillar. The cavity is shown to enhance the fraction of light that is resonantly scattered toward unity, generating antibunched indistinguishable photons that are 16 times narrower than the time-bandwidth limit, even when the transition is near saturation. Finally, deterministic excitation is used to create two-photon N00N states with which we make superresolving phase measurements in a photonic circuit.

Graphite Oxide to Graphene. Biomaterials to Bionics.

The advent of implantable biomaterials has revolutionized medical treatment, allowing the development of the fields of tissue engineering and medical bionic devices (e.g., cochlea implants to restore hearing, vagus nerve stimulators to control Parkinson's disease, and cardiac pace makers). Similarly, future materials developments are likely to continue to drive development in treatment of disease and disability, or even enhancing human potential. The material requirements for implantable devices are stringent. In all cases they must be nontoxic and provide appropriate mechanical integrity for the application at hand. In the case of scaffolds for tissue regeneration, biodegradability in an appropriate time frame may be required, and for medical bionics electronic conductivity is essential. The emergence of graphene and graphene-family composites has resulted in materials and structures highly relevant to the expansion of the biomaterials inventory available for implantable medical devices. The rich chemistries available are able to ensure properties uncovered in the nanodomain are conveyed into the world of macroscopic devices. Here, the inherent properties of graphene, along with how graphene or structures containing it interface with living cells and the effect of electrical stimulation on nerves and cells, are reviewed.

One-pot synthesis of ultra-small cerium oxide nanodots exhibiting multi-colored fluorescence.

CeO(2) nanodots of diameter 2nm have been synthesized by the thermolysis of cerium acetate in diphenylether in the presence of an oleic acid surfactant. The surfactant coating enabled them to be easily dispersible in nonpolar solvents. The CeO(2) dots exhibited size dependant optical properties such as a red shift in absorption and band gap. As a result, the surfactant coated CeO(2) nanocrystals emit photons in the visible region with broad photoluminescence spectra resulting in multi-colored fluorescence, which originates from defects associated with CeO(2) nanocrystals approaching molecular dimensions.

Biphasic synthesis of Au@SiO2 core-shell particles with stepwise ligand exchange.

We report the synthesis of well-dispersed core-shell Au@SiO(2) nanoparticles with minimal extraneous silica particle growth. Agglomeration was suppressed through consecutive exchange of the stabilizing ligands on the gold cores from citrate to L-arginine and finally (3-mercaptopropyl)triethoxysilane. The result was a vitreophilic, stable gold suspension that could be coated with silica in a biphasic mixture through controlled hydrolysis of tetraethoxysilane under L-arginine catalysis. Unwanted condensation of silica particles without gold cores was limited by slowing the transfer across the liquid-liquid interface and reducing the concentration of the L-arginine catalyst. In-situ dynamic light scattering and optical transmission spectroscopy revealed the growth and dispersion states during synthesis. The resulting core-shell particles were characterized via dynamic light scattering, optical spectroscopy, and electron microscopy. Their cores were typically 19 nm in diameter, with a narrow size distribution, and could be coated with a silica shell in multiple steps to yield core-shell particles with diameters up to 40 nm. The approach was sufficiently controllable to allow us to target a shell thickness by choosing appropriate precursor concentrations.