Rapid and Sensitive Quantification of the Pesticide Lindane by Polymer Modified Electrochemical Sensor.

Lindane is documented by the Environmental Protection Agency (EPA) as one of the most toxic registered pesticides. Conventional detection of lindane in the environment requires manual field sampling and complex, time-consuming analytical sample handling relying on skilled labor. In this study, an electrochemical sensing system based on a modified electrode is reported. The system is capable of detecting lindane in aqueous medium in only 20 s. The surface of a conventional carbon electrode is modified with a film of conductive polymer that enables detection of lindane down to 30 nanomolar. The electrode modification procedure is simple and results in a robust sensor that can withstand intensive use. The sensitivity of the sensor is 7.18 µA/µM and the performance was demonstrated in the determination of lindane in spiked ground water. This suggests that the sensor is potentially capable of providing useful readings for decision makers. The rapid and sensitive quantification of lindane in aqueous medium is one step forward to new opportunities for direct, autonomous control of the pesticide level in the environment.

Recent Development on the Electrochemical Detection of Selected Pesticides: A Focused Review.

Pesticides are heavily used in agriculture to protect crops from diseases, insects, and weeds. However, only a fraction of the used pesticides reaches the target and the rest slips through the soil, causing the contamination of ground- and surface water resources. Given the emerging interest in the on-site detection of analytes that can replace traditional chromatographic techniques, alternative methods for pesticide measuring have recently encountered remarkable attention. This review gives a focused overview of the literature related to the electrochemical detection of selected pesticides. Here, we focus on the electrochemical detection of three important pesticides; glyphosate, lindane and bentazone using a variety of electrochemical detection techniques, electrode materials, electrolyte media, and sample matrix. The review summarizes the different electrochemical studies and provides an overview of the analytical performances reported such as; the limits of detection and linearity range. This article highlights the advancements in pesticide detection of the selected pesticides using electrochemical methods and point towards the challenges and needed efforts to achieve electrochemical detection suitable for on-site applications.

Detection of Glyphosate in Drinking Water: A Fast and Direct Detection Method without Sample Pretreatment.

Glyphosate (Gly) is one of the most problematic pesticides that repeatedly appears in drinking water. Continuous on-site detection of Gly in water supplies can provide an early warning in incidents of contamination, before the pesticide reaches the drinking water. Here, we report the first direct detection of Gly in tap water with electrochemical sensing. Gold working electrodes were used to detect the pesticide in spiked tap water without any supporting electrolyte, sample pretreatment or electrode modifications. Amperometric measurements were used to quantify Gly to a limit of detection of 2 µM, which is below the regulation limit of permitted contamination of drinking water in the United States. The quantification of Gly was linearly proportional with the measured signal. The selectivity of this method was evaluated by applying the same technique on a Gly Metabolite, AMPA, and on another pesticide, omethoate, with a chemical structure similar to Gly. The testing revealed no interfering electrochemical activity at the potential range used for Gly detection. The simple detection of Gly presented in this work may lead to direct on-site monitoring of Gly contamination at drinking water sources.

Marine-terminating glaciers sustain high productivity in Greenland fjords.

Accelerated mass loss from the Greenland ice sheet leads to glacier retreat and an increasing input of glacial meltwater to the fjords and coastal waters around Greenland. These high latitude ecosystems are highly productive and sustain important fisheries, yet it remains uncertain how they will respond to future changes in the Arctic cryosphere. Here we show that marine-terminating glaciers play a crucial role in sustaining high productivity of the fjord ecosystems. Hydrographic and biogeochemical data from two fjord systems adjacent to the Greenland ice sheet, suggest that marine ecosystem productivity is very differently regulated in fjords influenced by either land-terminating or marine-terminating glaciers. Rising subsurface meltwater plumes originating from marine-terminating glaciers entrain large volumes of ambient deep water to the surface. The resulting upwelling of nutrient-rich deep water sustains a high phytoplankton productivity throughout summer in the fjord with marine-terminating glaciers. In contrast, the fjord with only land-terminating glaciers lack this upwelling mechanism, and is characterized by lower productivity. Data on commercial halibut landings support that coastal regions influenced by large marine-terminating glaciers have substantially higher marine productivity. These results suggest that a switch from marine-terminating to land-terminating glaciers can substantially alter the productivity in the coastal zone around Greenland with potentially large ecological and socio-economic implications.

Glacier retreat alters downstream fjord ecosystem structure and function in Greenland.

The melting of the Greenland Ice Sheet is accelerating, with glaciers shifting from marine to land termination and potential consequences for fjord ecosystems downstream. Monthly samples in 2016 in two fjords in southwest Greenland show that subglacial discharge from marine-terminating glaciers sustains high phytoplankton productivity that is dominated by diatoms and grazed by larger mesozooplankton throughout summer. In contrast, melting of land-terminating glaciers results in a fjord ecosystem dominated by bacteria, picophytoplankton and smaller zooplankton, which has only one-third of the annual productivity and half the CO2 uptake compared to the fjord downstream from marine-terminating glaciers.

Hydrology-linked spatial distribution of pesticides in a fjord system in Greenland.

A pilot study is presented evaluating selected chlorinated pesticides as chemical tracers for water masses in a sub-Arctic fjord system (Godthåbsfjord, western Greenland). Polyoxymethylene (POM) based passive water samplers were deployed during summer-autumn 2010. The levels of the analysed chlorinated pesticides in the fjord surface waters were found to be low compared to earlier studies. α-Hexachlorocyclohexane (α-HCH) and hexachlorobenzene (HCB) were the predominant contaminants. However, these two compounds have higher levels in oceanic water compared to freshwater influenced fjord waters. These chemicals can thus be considered as indicators for direct atmospheric long-range transport, while the organochlorine pesticides like trans-, cis-chlordane, trans-nonachlor and oxychlordane that are detected in the inner parts of the fjord are indicators for potential freshwater sources such as rivers and glacial meltwater runoff (secondary sources). The average values were 50 pg L(-1) for HCB and 11 pg L(-1) for α-HCH. These concentrations are comparable to levels in fjords in Svalbard (Norwegian Arctic), but lower than in open and/or ice covered oceans in the Canadian Arctic. Two air samplers were deployed for the identification of direct atmospheric contributions. Local contamination sources do not contribute significantly. The study demonstrated the value of passive water sampling devices for comprehensive hydrological characterization of Arctic coastal waters.

Electrochemical determination of bentazone using simple screen-printed carbon electrodes.

Bentazone is one of the most problematic pesticides polluting groundwater resources. It is on the list of pesticides that are mandatory to analyze at water work controls. The current pesticide measuring approach includes manual water sampling and time-consuming chromatographical quantification of the bentazone content at centralized laboratories. Here, we report the use of an electrochemical approach for analytical determination of bentazone that takes 10 s. The electrochemical electrodes were manually screen printed, resulting in the low-cost fabrication of the sensors. The current response was linearly proportional to the bentazone concentration with a R2 ~ 0.999. We demonstrated a sensitivity of 0.0987 µA/µM and a limit of detection of 0.034 µM, which is below the U.S. Health Advisory level. Furthermore, the sensors have proved to be reusable and stable with a drop of only 2% after 15 times reuse. The sensors have been applied to successfully quantify bentazone spiked in real groundwater and lake water. The sensing method presented here is a step towards on-site application of electrochemical detection of pesticides in water sources.

n-3 PUFA biosynthesis by the copepod Apocyclops royi documented using fatty acid profile analysis and gene expression analysis.

The cyclopoid copepod Apocyclops royi (Lindberg 1940) is one of two dominant mesozooplankton species in brackish Taiwanese aquaculture ponds. Periodically low n-3 polyunsaturated fatty acid (PUFA) content in seston could potentially be a limiting factor for zooplankton diversity. Apocyclops royi's potential ability to biosynthesize n-3 PUFA was investigated through a short-term feeding experiment on four species of microalgae. Furthermore, we analyzed the expression of genes encoding putative fatty acid elongase (ELO) and desaturase (FAD) enzymes in A. royi on long-term diets of the PUFA-poor Dunaliella tertiolecta and the PUFA-rich Isochrysis galbana The copepods exhibited high contents of docosahexaenoic acid (DHA, C22:6n-3) (>20% of total fatty acid) even when DHA-starved for two generations, and no significant differences were found in absolute DHA content between treatments. Transcripts correlating to the four enzymes Elovl4, Elovl5, Fad Δ5 and Fad Δ6 in the n-3 PUFA biosynthetic pathway were identified. Gene expression analysis revealed a significantly higher expression of two desaturases similar to Fad Δ6 in copepods fed PUFA-lacking algae compared to copepods fed algae with high PUFA content. These findings suggest a highly active n-3 PUFA biosynthesis and capability of DHA production in A. royi when fed low-PUFA diets.

High geothermal heat flux in close proximity to the Northeast Greenland Ice Stream.

The Greenland ice sheet (GIS) is losing mass at an increasing rate due to surface melt and flow acceleration in outlet glaciers. Currently, there is a large disagreement between observed and simulated ice flow, which may arise from inaccurate parameterization of basal motion, subglacial hydrology or geothermal heat sources. Recently it was suggested that there may be a hidden heat source beneath GIS caused by a higher than expected geothermal heat flux (GHF) from the Earth's interior. Here we present the first direct measurements of GHF from beneath a deep fjord basin in Northeast Greenland. Temperature and salinity time series (2005-2015) in the deep stagnant basin water are used to quantify a GHF of 93 ± 21 mW m-2 which confirm previous indirect estimated values below GIS. A compilation of heat flux recordings from Greenland show the existence of geothermal heat sources beneath GIS and could explain high glacial ice speed areas such as the Northeast Greenland ice stream.

Paper-based sensors for rapid detection of virulence factor produced by Pseudomonas aeruginosa.

Pyocyanin is a toxin produced by Pseudomonas aeruginosa. Here we describe a novel paper-based electrochemical sensor for pyocyanin detection, manufactured with a simple and inexpensive approach based on electrode printing on paper. The resulting sensors constitute an effective electrochemical method to quantify pyocyanin in bacterial cultures without the conventional time consuming pretreatment of the samples. The electrochemical properties of the paper-based sensors were evaluated by ferri/ferrocyanide as a redox mediator, and showed reliable sensing performance. The paper-based sensors readily allow for the determination of pyocyanin in bacterial cultures with high reproducibility, achieving a limit of detection of 95 nM and a sensitivity of 4.30 µA/µM in standard culture media. Compared to the similar commercial ceramic based sensors, it is a 2.3-fold enhanced performance. The simple in-house fabrication of sensors for pyocyanin quantification allows researchers to understand in vitro adaptation of P. aeruginosa infections via rapid screenings of bacterial cultures that otherwise are expensive and time-consuming.

Evidence of local and regional freshening of Northeast Greenland coastal waters.

The supply of freshwater to fjord systems in Greenland is increasing as a result of climate change-induced acceleration in ice sheet melt. However, insight into the marine implications of the melt water is impaired by lack of observations demonstrating the fate of freshwater along the Greenland coast and providing evaluation basis for ocean models. Here we present 13 years of summer measurements along a 120 km transect in Young Sound, Northeast Greenland and show that sub-surface coastal waters are decreasing in salinity with an average rate of 0.12 ± 0.05 per year. This is the first observational evidence of a significant freshening on decadal scale of the waters surrounding the ice sheet and comes from a region where ice sheet melt has been less significant. It implies that ice sheet dynamics in Northeast Greenland could be of key importance as freshwater is retained in southward flowing coastal currents thus reducing density of water masses influencing major deep water formation areas in the Subarctic Atlantic Ocean. Ultimately, the observed freshening could have implications for the Atlantic meridional overturning circulation.

Sea ice breakup and marine melt of a retreating tidewater outlet glacier in northeast Greenland (81°N).

Rising temperatures in the Arctic cause accelerated mass loss from the Greenland Ice Sheet and reduced sea ice cover. Tidewater outlet glaciers represent direct connections between glaciers and the ocean where melt rates at the ice-ocean interface are influenced by ocean temperature and circulation. However, few measurements exist near outlet glaciers from the northern coast towards the Arctic Ocean that has remained nearly permanently ice covered. Here we present hydrographic measurements along the terminus of a major retreating tidewater outlet glacier from Flade Isblink Ice Cap. We show that the region is characterized by a relatively large change of the seasonal freshwater content, corresponding to ~2 m of freshwater, and that solar heating during the short open water period results in surface layer temperatures above 1 °C. Observations of temperature and salinity supported that the outlet glacier is a floating ice shelf with near-glacial subsurface temperatures at the freezing point. Melting from the surface layer significantly influenced the ice foot morphology of the glacier terminus. Hence, melting of the tidewater outlet glacier was found to be critically dependent on the retreat of sea ice adjacent to the terminus and the duration of open water.

Preoperative chemoradiation of locally advanced T3 rectal cancer combined with an endorectal boost.

PURPOSE: To investigate the effect and feasibility of concurrent radiation and chemotherapy combined with endorectal brachytherapy in T3 rectal cancer with complete pathologic remission as end point. METHODS AND MATERIALS: The study included 50 patients with rectal adenocarcinoma. All patients had T3 tumor with a circumferential margin 0-5 mm on a magnetic resonance imaging scan. The radiotherapy was delivered by a technique including two planning target volumes. Clinical target volume 1 (CTV1) received 60 Gy/30 fractions, and CTV2 received 48.6 Gy/27 fractions. The tumor dose was raised to 65 Gy with endorectal brachytherapy 5 Gy/1 fraction to the tumor bed. On treatment days, the patients received uracil and tegafur 300 mg/m2 concurrently with radiotherapy. RESULTS: Forty-eight patients underwent operation. Histopathologic tumor regression was assessed by the Tumor Regression Grade (TRG) system. TRG1 was recorded in 27% of the patients, and a further 27% were classified as TRG2. TRG3 was found in 40%, and 6% had TRG4. The toxicity was low. CONCLUSION: The results indicate that high-dose radiation with concurrent chemotherapy and endorectal brachytherapy is feasible with a high rate of complete response, but further trials are needed to define its possible role as treatment option.

Recent increases in Arctic freshwater flux affects Labrador Sea convection and Atlantic overturning circulation.

The Atlantic Meridional Overturning Circulation (AMOC) is an important component of ocean thermohaline circulation. Melting of Greenland's ice sheet is freshening the North Atlantic; however, whether the augmented freshwater flux is disrupting the AMOC is unclear. Dense Labrador Sea Water (LSW), formed by winter cooling of saline North Atlantic water and subsequent convection, is a key component of the deep southward return flow of the AMOC. Although LSW formation recently decreased, it also reached historically high values in the mid-1990s, making the connection to the freshwater flux unclear. Here we derive a new estimate of the recent freshwater flux from Greenland using updated GRACE satellite data, present new flux estimates for heat and salt from the North Atlantic into the Labrador Sea and explain recent variations in LSW formation. We suggest that changes in LSW can be directly linked to recent freshening, and suggest a possible link to AMOC weakening.

Chromatographic preprocessing of GC-MS data for analysis of complex chemical mixtures.

Hyphenated analytical techniques such as gas chromatography-mass spectrometry (GC-MS) can provide extensive amounts of analytical data when applied to environmental samples. Quantitative analyses of complex contaminant mixtures by commercial preprocessing software are time-consuming, and baseline distortion and incomplete peak resolution increase the uncertainty and subjectivity of peak quantification. Here, we present a semi-automatic method developed specific for processing complex first-order chromatographic data (e.g. selected ion monitoring in GC-MS) prior to chemometric data analysis. Chromatograms are converted into semi-quantitative variables (e.g. diagnostic ratios (DRs)) that can be exported directly to appropriate softwares. The method is based on automatic peak matching, initial parameterization, alternating background noise reduction and peak estimation using mathematical functions (Gaussian and exponential-Gaussian hybrid) with few (i.e. three to four) parameters. It is capable of resolving convoluted peaks, and the exponential-Gaussian hybrid improves the description of asymmetric peaks (i.e. fronting and tailing). The optimal data preprocessing suggested in this article consists of estimation of Gaussian peak parameters and subsequent calculation of diagnostic ratios from peak heights. We tested the method on chromatographic data from 20 replicate oil samples and found it to be less time-consuming and subjective than commercial software, and with comparable data quality.

Multivariate statistical methods for evaluating biodegradation of mineral oil.

Two methods were developed for evaluating natural attenuation and bioremediation of mineral oil after environmental spills and during in vitro experiments. Gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode was used to obtain compound-specific data. The chromatographic data were then preprocessed either by calculating the first derivative, retention time alignment and normalization or by peak identification, quantification and calculation of diagnostic ratios within homologue series of polycyclic aromatic compounds (PACs). Finally, principal component analysis (PCA) was applied to the preprocessed chromatograms or diagnostic ratios to study the fate of the oil. The methods were applied to data from an in vitro biodegradation experiment with a North Sea crude oil exposed to three mixtures of bacterial strains: R (alkane degraders and surfactant producers), U (PAC degraders) and M (mixture of R- and U-strains) over a 1-year-period with five sampling times. Assessment of variation in degradability within isomer groups of methylfluorenes (m/z 180), methylphenanthrenes (m/z 192) and methyldibenzothiophenes (m/z 198) was used to evaluate the effects of microbial degradation on the composition of the oil. The two evaluation methods gave comparable results. In the objective pattern matching approach, principal component 1 (PC1) described the general changes in the isomer abundances, whereas M samples were separated from U and R samples along PC2. Furthermore, in the diagnostic ratio approach, a third component (PC3) could be extracted; although minor, it separated R samples from U and M samples. These results demonstrated that the two methods were able to differentiate between the effects due to the different bacterial activities, and that bacterial strain mixtures affected the PAC isomer patterns in different ways in accordance with their different metabolic capabilities.

[Adjuvant chemotherapy for patients with rectal cancer]. / Adjuverende kemoterapi til patienter med rectumcancer--en gennemgang af et Cochranereview.

A new Cochrane meta-analysis evaluated adjuvant chemotherapy (5-fluorouracil (5FU)-based, not modern combination chemotherapy) in almost 10,000 patients with rectal cancer and showed a 17% reduction in mortality corresponding well to the efficacy observed in recent studies, which reported a reduction in mortality just about 20%. The authors recommend adjuvant chemotherapy which is in accordance with the Danish national guidelines where 5-FU-based chemotherapy is recommended for stage III and high-risk stage II rectal cancer.

Electrodialytic soil remediation enhanced by low frequency pulse current--overall chronopotentiometric measurement.

The effect of low frequency pulse current on decreasing the polarization and energy consumption during the process of electrodialytic soil remediation was investigated in the present work. The results indicated that the transportation of cations through the cation exchange membrane was the rate controlling step both in constant and pulse current experiments, thus responsible for the major energy consumption. After 180 h, a decrease in both the initial ohmic resistance in each pulse cycle and the resistance caused by concentration polarization of the anion exchange membrane were seen in the pulse current experiment compared to the constant current experiment. At the cation exchange membrane, only the resistance caused by concentration polarization decreased. In the soil compartment, an average of +60 mV overpotential caused by the polarization of the electric double layer of the clay particles was obtained from the Nernstian behavior simulation of the relaxation process, which was significantly lower than the ohmic voltage drop induced by pore fluid resistance. Therefore, the ohmic polarization was the major contributor to the energy consumption in the soil compartment and diminished by pulse current.

Interaction free energies of eight sodium salts and a phosphatidylcholine membrane.

Many recent reports have discussed specific effects of anions on the properties of lipid membranes and possible roles of such effects within biochemistry. One key parameter in both theoretical and experimental treatments of membrane-salt interactions is the net affinity, that is, the free energy of interaction. This parameter has been analyzed theoretically and by modeling of experimental data but not directly measured even for simple salt-membrane systems. To provide such information, we have studied the interaction of unilamellar liposomes of dimyristoyl phosphatidylcholine (DMPC) and eight sodium salts by dialysis equilibrium measurements. This method provides model free thermodynamic data and allows investigations in the dilute concentration range where solution nonideality and perturbation of membrane structure is limited. The transfer free energy of DMPC from water to salt solutions, Δµ(2,trans), was found to scale proportionally to the salt concentration, m(3), in the 0-50 mmolal range, and we suggest that the slope, Δµ(2,trans)/(out)m(3), represents an experimental salt-membrane interaction potential. The values of Δµ(2,trans)/(out)m(3) for sodium salts of monovalent anions ranged from +2.2 kJ (mol·molal)(-1) for F(-) to -16.9 kJ (mol·molal)(-1) for SCN(-), thus confirming a distinct membrane specificity among the anions. For Na(2)SO(4), the interaction was strongly unfavorable with Δµ(2,trans)/(out)m(3) = +20.6 kJ (mol·molal)(-1). The dialysis data were supplemented with calorimetric measurements and analyzed with respect to a two-domain model.