Highly Permeable Monolith-based Multichannel In-Tip Microextraction Apparatus for Simultaneous Field Sample Preparation of Pesticides and Heavy Metal Ions in Environmental Waters.

A portable multichannel in-tip microextraction-based field sample preparation (FSP) apparatus was developed using polymer-based monoliths as an extraction phase. The construction of the FSP device is quite facile and convenient. More specifically, according to the chemical properties of studied analytes, functional-rich and high-permeability monoliths were in situ synthesized in pipet tips. After that, three tips containing the sorbents were mounted to three syringes, which were connected to a screw motor employed to drive the syringes and accurately regulate the flow rates in the adsorption and desorption stages. Because of the multifunction groups in the monoliths, the sorbents displayed satisfactory coextraction performance for pesticides (carbamates and triazoles) and heavy metal ions (Cd2+, Pb2+, and Cu2+) under the optimized conditions. The practicability of the proposed apparatus was demonstrated by the quick and simultaneous FSP of studied analytes in various environmental waters and combined with high-performance liquid chromatography/diode-array detection (for pesticides) and atomic absorption spectrometry (for metal ion) analysis. The results indicated that the limits of detection for the pesticides and metal ions were in the range of 0.36 to 1.2 ng/L and 0.061 to 0.40 ng/L, respectively, with ideal coefficients of determination. Furthermore, the results obtained with the constructed device were quite comparable to those obtained with the traditional laboratory extraction process, which demonstrated that the newly developed apparatus possesses the expected application in the high-throughput FSP of pesticides and heavy metal ions in water samples.

A Novel Active Sampler Coupling Osmotic Pump and Solid Phase Extraction for in Situ Sampling of Organic Pollutants in Surface Water.

Active samplers for ambient monitoring of trace contaminants in surface water are highly desirable, but their use is often constrained by power supply. Here, we proposed a novel solution by coupling an improved osmotic pump (OP) with a solid-phase extraction (SPE) cartridge to construct a power-free active sampler for organic contaminants. The OP simply consisted of two cylindrical chambers separated by a reverse osmosis membrane. We, for the first time, added ion-exchange resins into the OP inlet chamber and successfully constructed OPs with a smooth and constant flow. In the OP-SPE sampler, water was continuously drawn through the SPE cartridge at a constant flow, and time-weighted average concentration over the sampling course may be easily calculated from the amount of target analytes retained on the SPE cartridge and water collected in the sampler. The OP-SPE samplers were deployed in a river to detect herbicides, and the measured concentrations were largely in agreement with the average of 11 daily spot samples. Given that a wide range of SPE cartridges are available for different classes of organic contaminants, this approach is versatile and may find widespread applications for in situ sampling of surface water under different conditions, including poorly accessible locations.

Single-layer graphene prevents Cassie-wetting failure of structured hydrophobic surface for efficient condensation.

HYPOTHESIS: Structured hydrophobic surfaces often suffer from Cassie-wetting failure due to trapped water in structure gaps for a long-term operation. Sustainable Cassie-wetting on such surface could be achieved by coating an atom-thick and moisture-impermeable graphene on it. EXPERIMENTS: Water contact angles were measured to clarify the effect of graphene on wetting, and water impermeability was verified by moisture deposition and evaporation. Sliding angle measurements and vapor condensation were carried out to demonstrate the stable Cassie-state wetting and application. FINDINGS: Interestingly we found the graphene does not significantly disrupt the wetting behavior of the structured hydrophobic surface, showing a wettability transparency. Moreover, the impermeability of graphene keeps moisture away from the structure gaps. Owning to the combination of these two properties, droplets on the graphene-coated structured surface exhibit a stable Cassie-state hydrophobic wetting, even under the situation of moisture deposition and evaporation. Using the modified surface, we also found a 40-100% increase in condensation efficiency for a 5-hour vapor condensation at a subcooling of 40 °C. These results suggest an effective strategy to prevent Cassie-wetting failure of structured hydrophobic surface and are expected to promote its further application in more complex conditions.

Time-series sampling of trace metals in surface waters using osmotic sampler with air segmentation and preservative addition.

High-resolution time-series concentrations (CTS) are very important for the investigation of the biogeochemical processes of trace metals in the aquatic environment. However, the acquisition of CTS of trace metals in water is still challenging because of the lack of suitable samplers. In this study, an osmotic sampler coupled with air segment injection and preservative addition was employed for time-series sampling of trace metals in surface waters. In the sampler, water sampling and preservative adding are both driven by osmotic pumps (OPs), while air segment injection is accomplished by a timer-controlled micro diaphragm pump. During deployment, the sampling OP continuously draws water through a filter and stores it in a narrow-bore coil. Simultaneously, a preservative OP slowly pushes 30% HNO3 (v/v) into the collected sample for in situ preservation. Periodically, the micro diaphragm pump injects air into the continuous water stream to divide it into water segments, enabling accurate time-stamping. After retrieval, the time-series samples were pumped out from the coil and re-collected to analyze the CTS of analytes. The sampler was deployed in river, reservoir, and marine waters for 26 h and one week to measure CTS of trace metals at time resolutions of 2 h and 12 h. Results showed that the recoveries of a preloaded standard mixture (1.0 µg/L) in all samplers ranged from 93.1% to 117.8%. The measured CTS of Cd, Co, Cr, Cu, Mn, and Ni in the waters only varied in small ranges. Accordingly, the measured CTS data from the sampler were consistent with the obtained concentrations from grab sampling. The relative percent differences between the measurements from two samplers were less than 37.4%. These results demonstrate the reliability and accuracy of the sampler for time-series sampling of the chosen trace metals in surface waters.

Measuring of time-series concentrations of nutrients in surface waters using osmotic sampler with air bubble segmentation and preservative addition.

The analysis of time-series concentrations (CTS) is of great importance when investigating the biogeochemical processes of nutrients in aquatic environments. However, obtaining CTS of nutrients remains a challenge using current sampling techniques. In this study, a novel in situ sampler was constructed using reverse osmosis membrane (ROM) osmotic pumps (OP) (ROM-OP sampler), and was used to obtain the CTS of nutrients in surface waters. The sampler consisted of a sampling OP, sample storing coil, filter, bubble injection module, and preservative adding module. When deployed, the sampling OP continuously draws ambient water through the filter into the sample storing coil, while simultaneously the preservative adding module continuously delivers preservative (H2SO4 solution) into the water flow. The bubble injection module periodically injects air bubbles into the sample storing coil, to segment the sample and create time stamp indicators that allow the sample age to be defined. Upon retrieval, the sample segments in the coil are sequentially pumped out of the sample storing coil and transferred into different vials for further analysis. The sampler was applied to measure the CTS of various nutrients, including dissolved total nitrogen, dissolved total phosphorus, dissolved reactive phosphorus, and nitrate in a river over a 20 day period and in municipal sewage treatment plant effluent for a 36 h period. Results showed that the ROM-OP sampler successfully obtained CTS of nutrients, capturing nutrient variations at a high temporal resolution. This sampler is relatively low-cost (~USD 300), small in size, lightweight, robust and does not require an external power source, showing high promise as an effective and efficient tool for monitoring nutrient CTS in aquatic environments.

Polymeric ionic liquid-based portable tip microextraction device for on-site sample preparation of water samples.

On-site sample preparation is highly desired because it avoids the transportation of large-volume samples and ensures the accuracy of the analytical results. In this work, a portable prototype of tip microextraction device (TMD) was designed and developed for on-site sample pretreatment. The assembly procedure of TMD is quite simple. Firstly, polymeric ionic liquid (PIL)-based adsorbent was in-situ prepared in a pipette tip. After that, the tip was connected with a syringe which was driven by a bidirectional motor. The flow rates in adsorption and desorption steps were controlled accurately by the motor. To evaluate the practicability of the developed device, the TMD was used to on-site sample preparation of waters and combined with high-performance liquid chromatography with diode array detection to measure trace estrogens in water samples. Under the most favorable conditions, the limits of detection (LODs, S/N = 3) for the target analytes were in the range of 4.9-22 ng/L, with good coefficients of determination. Confirmatory study well evidences that the extraction performance of TMD is comparable to that of the traditional laboratory solid-phase extraction process, but the proposed TMD is more simple and convenient. At the same time, the TMD avoids complicated sampling and transferring steps of large-volume water samples.

Simultaneous determination of total dissolved nitrogen and total dissolved phosphorus in natural waters with an on-line UV and thermal digestion.

A flow injection method combined with an on-line UV and thermal digestion for simultaneous determination of total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP) in natural waters was established in this study. A novel flow manifold made the proposed system compact and automatic. The conversion rates of various nitrogen and phosphorus compounds to their nitrate and phosphate forms with different digestion models and different concentrations were well investigated using the flow injection technique. The reagent concentrations for colorimetric analysis were optimized based on a univariate experimental design. The detection limits were 0.8 µmol L-1 and 0.2 µmol L-1, and linear analytical ranges were up to 300 µmol L-1 and 25 µmol L-1 for TDN and TDP, respectively. The sample throughput was ~ 5 h-1. The recovery of spiked natural water samples varied from 86.8% to 102.6% for TDN and 88.0% to 102.0% for TDP. The present approach was successfully applied for the determination of TDN and TDP in natural water samples and was found to have good agreement with reference methods. The outcomes of present study indicated that the proposed method is suitable for routine analysis as well as for potential on-line monitoring.