Environmental monitoring of hydrocarbons: a chemical sensor perspective

Assessing the environmental impact of organic pollutants requires reliable analytical tools that can rapidly screen them with minimal sample handling. Chemical sensors are expected to play an increasing role in environmental monitoring, and recent technological advances are certain to facilitate the application of chemical sensing devices. The search for highly selective, sensitive, low cost, stable, and robust sensors for hydrocarbons is an area of interest that is reflected by many publications on this topic. This report surveys some of the work that has been undertaken using sensors to detect hydrocarbons in the gas and liquid phase. The analytical capabilities of various sensors are compared and discussed in terms of their selectivity, sensitivity, and detection limit. It was found that the sensitivity is highly dependent on the experimental conditions used in the preparation of the sensing surface. Many sensors display acceptable sensitivity under controlled laboratory conditions; however, very few are selective enough to distinguish among several hydrocarbons in complex mixtures. Selectivity is still a challenge that is hindering the widespread application of chemical sensors for environmental monitoring of hydrocarbons and a number of strategies have been proposed to help overcome some of these problems.     

Greatly enhanced arsenic shoot assimilation in rice leads to elevated grain levels compared to wheat and barley

Paired grain, shoot, and soil of 173 individual sample sets of commercially farmed temperate rice, wheat, and barley were surveyed to investigate variation in the assimilation and translocation of arsenic (As). Rice samples were obtained from the Carmargue (France), Do?ana (Spain), Cadiz (Spain), California, and Arkansas. Wheat and barleywere collected from Cornwall and Devon (England) and the east coast of Scotland. Transfer of As from soil to grain was an order of magnitude greater in rice than for wheat and barley, despite lower rates of shoot-to-grain transfer. Rice grain As levels over 0.60 microg g(-1) d. wt were found in rice grown in paddy soil of around only 10 microg g(-1) As, showing that As in paddy soils is problematic with respect to grain As levels. This is due to the high shoot/soil ratio of approximately 0.8 for rice compared to 0.2 and 0.1 for barley and wheat, respectively. The differences in these transfer ratios are probably due to differences in As speciation and dynamics in anaerobic rice soils compared to aerobic soils for barley and wheat. In rice, the export of As from the shoot to the grain appears to be under tight physiological control as the grain/shoot ratio decreases by more than an order of magnitude (from approximately 0.3 to 0.003 mg/kg) and as As levels in the shoots increase from 1 to 20 mg/kg. A down regulation of shoot-to-grain export may occur in wheat and barley, but it was not detected at the shoot As levels found in this survey. Some agricultural soils in southwestern England had levels in excess of 200 microg g(-1) d. wt, although the grain levels for wheat and barley never breached 0.55 microg g(-1) d. wt. These grain levels were achieved in rice in soils with an order of magnitude lower As. Thus the risk posed by As in the human food-chain needs to be considered in the context of anaerobic verses aerobic ecosystems.     

Treating smokers before the quit date: can nicotine patches and denicotinized cigarettes reduce cravings?

The present study investigated whether treatment with the combination of denicotinized cigarettes and 21-mg nicotine patch for 2 weeks before a designated quit date could lessen cravings for smoking, thereby helping smokers abstain from smoking. The study was a randomized controlled clinical trial conducted at Roswell Park Cancer Institute, Buffalo, New York, in 2004 and 2005. Patients included 98 adult heavy smokers (using 20 or more cigarettes/day). Half of the subjects received 2 weeks of combination of denicotinized cigarettes (Quest 3) and 21-mg nicotine patch for 2 weeks before the quit date. The remaining smokers were switched to light cigarettes (Quest 1) during the 2 weeks before the quit date. After the quit date, all subjects received counseling for smoking cessation and were provided nicotine patches for up to 8 weeks after the quit date. Self-reported cravings for smoking, withdrawal symptoms, and smoking abstinence were measured at predetermined intervals using phone-based surveys and in clinical visits. The group that used denicotinized cigarettes and nicotine patch before quitting reported less frequent and less intense cravings for cigarettes in the 2 weeks before and after the designated quit date. Self-reported withdrawal symptoms and quit rates did not differ significantly between the groups. The use of a denicotinized cigarette combined with the nicotine patch appears to lessen cravings to smoke in the immediate postcessation period. A larger, better-powered study is needed to test if this treatment combination has merit for increasing quit rates.     

Unsaturated zone arsenic distribution and implications for groundwater contamination

Arsenic compounds have been applied at the land surface as pesticides in agricultural areas globally. The purpose of this study was to evaluate the fate of anthropogenic arsenic applications related to agriculture, using arsenic applications on cotton in the southern High Plains (SHP), Texas, as a case study and examining possible linkages with contamination of the underlying Ogallala aquifer in this region, where 36% of wells exceed the new EPA 10 microg/L standard. Unsaturated zone soil samples were collected from boreholes beneath natural ecosystems (grassland/ shrubland) to provide a control (no arsenic application) (5 profiles) and cotton cropland (20 profiles) for analyses of water-extractable arsenic, vanadium, phosphate, chloride, and nitrate. Natural ecosystem profiles have high arsenic concentrations at depth (maximum of 7.2-69.6 microg As/ kg dry soil at 5.9-21.4 m depth) that are attributed to a geologic source. Most profiles beneath cotton cropland have high arsenic concentrations within the upper meter (profile means 1.7 to 31.6 microg/kg) that correlate with phosphate (r = 0.70, p < 0.01) and are attributed to anthropogenic arsenic application associated with phosphate fertilizer application. High arsenic concentrations at >1 m depth (profile means < or =36.3 microg/kg) found in cropland profiles are attributed to a geologic source because of similarity with profiles beneath natural ecosystems, lack of correlation with phosphate, and pore-water ages that predate anthropogenic arsenic application in many profiles. GIS analyses showed poor correlations between groundwater arsenic and percent cultivated land (r = -0.15, p < 0.01), groundwater nitrate (r = 0.30, p < 0.01), and water table depth (r= -0.31, p < 0.01), further supporting the idea that anthropogenic-derived arsenic in the shallow subsurface is not linked to groundwater arsenic contamination in this region.     

Sedimentary records of DDT and HCH in the Pearl River Delta,South China

Tropical regions in developing countries are thought to be significant sources of organochlorine pesticides in the global context, owing to high rate of use and only a recent production ban or restriction on application of these pesticides. In the present paper, DDT and HCH in eight 210Pb-dated sedimentary cores from the Pearl River Delta, South China, were analyzed in order to reconstruct the time trends of these persistent organic pollutants in this tropical region. The sedimentary inventories of sigmaDDT and sigmaHCH through the cores ranged from 36.6 to 1109.5 ng/cm2 and from 11.2 to 226.3 ng/cm2, respectively, and their spatial distribution implies that the water flows from the Humen, Jiaomen, Hongqili, and Hengmen outlets rather than the Xijiang flow from Modaomen outlet, supplied the major historical input of DDT to the estuary. Although a production ban of technical HCH and DDT was imposed in China in 1983, their sedimentary fluxes display increasing trends or strong rebounds in the 1990s as recorded in the core profiles, characteristic of the increasing ratios of (DDE + DDD)/DDT and DDE/DDT. It is suggested that an enhanced land soil runoff in the process of large-scale land transform, as well as a higher river water flow in early 1990s, had mobilized these pesticides from soil to the sedimentary system in the region.     

Measurement and dynamic modeling of trace metal mobilization in soils using DGT and DIFS

The technique of diffusive gradients in thin-films (DGT) accumulates metals on a Chelex resin after their diffusive transport through a hydrogel. It lowers metal concentrations in soil solution adjacent to the device and induces resupply of metal associated with the solid phase. DGT devices were deployed in an alluvial gley soil for 21 different time periods between 4 h and 19.5 d. The accumulated masses of Cu, Cd, Ni, and Zn were used to calculate the distribution coefficient for labile metal, Kdl, and adsorption and desorption rate constants. Calculations were performed using a dynamic numerical model of DGT-induced fluxes in soils (DIFS). It assumes first-order exchange between solid phase and solution and diffusional transport in both the soil solution and the hydrogel. The DIFS model fitted changes in accumulated mass with time very well. Values of Kdl calculated from DIFS of 100 (Cd), 250 (Cu), 150 (Ni), and 150 (Zn) were larger than values of distribution coefficients estimated by exchange with Ca(NO3)2 but similar to those estimated by isotopic exchange (Cd and Zn only). These results suggest that the solid-phase pool of metal affected by the removal of labile metal by DGT, which operates on a time scale of minutes, is similar to the solid-phase pool of metal that can isotopically exchange with solution on a time scale of 2 d. Response times of minutes were consistent with interaction rates with surfaces, and desorption rate constants agreed with other reported values. An appraisal of the DIFS model demonstrated the importance of the labile pool size in the solid phase for controlling supply to a sink, such as DGT or a plant. As values of Kdl and kinetic parameters are obtained using DGT with minimal soil disturbance and by a similar mechanism to that involved in plant uptake, they may be pertinent to bioavailability studies.     

Density-modified displacement for DNAPL source zone remediation: density conversion and recovery in heterogeneous aquifer cells

Low interfacial tension (IFT) displacement (mobilization) of nonaqueous phase liquids (NAPLs) offers potential as an efficient remediation technology for contaminated aquifer source zones. However, displacement of dense NAPLs (DNAPLs) is problematic due to the tendency for downward migration and redistribution of the mobilized DNAPL. To overcome this limitation, a density-modified displacement method (DMD) was developed, which couples in situ density conversion of DNAPLs via alcohol partitioning with low IFT NAPL displacement and recovery. The objective of this work was to evaluate the DMD method for two representative DNAPLs, chlorobenzene (CB) and trichloroethene (TCE). Laboratory-scale experiments were conducted in a two-dimensional (2-D) cell, configured to represent a heterogeneous unconfined aquifer system containing low permeability lenses. After release and redistribution of either CB- or TCE-NAPL, the 2-D aquifer cells were flushed with a 6% (wt) n-butanol aqueous solution to achieve DNAPL to light NAPL conversion, followed by a low IFT surfactant solution consisting of 4% (4:1) Aerosol MA/Aerosol OT + 20% n-butanol + 500 mg/L CaCl2. Visual observations and experimental measurements demonstrated that in situ density conversion and immiscible displacement of both CB and TCE were successful. Effluent NAPL densities ranged from 0.96 to 0.90 g/mL for CB and from 0.95 to 0.92 g/mL for TCE, while aqueous phase densities remained above 0.96 g/L. Density conversion of CB and TCE was achieved after flushing with 1.2 and 4.9 pore vol of 6% n-butanol solution, respectively. Recoveries of 90% CB and 85% TCE were realized after flushing with 1.2 pore vol of the low IFT surfactant solution, which was followed by a 1 pore vol posttreatment water flood. Surfactant and n-butanol recoveries ranged from 75 to 96% based on effluent concentration data. The observed minimal mobilization during the n-butanol density conversion preflood and near complete mobilization during the low IFT displacement flood were consistent with total trapping number calculations. The results reported herein demonstrate the potential efficiency of the DMD technology as a means of DNAPL source zone restoration.     

A hierarchical modeling approach for estimating national distributions of chemicals in public drinking water systems

Water quality studies often include the analytical challenge of incorporating censored data and quantifying error of estimation. Many analytical methods exist for estimating distribution parameters when censored data are present. This paper presents a Bayesian-based hierarchical model for estimating the national distribution of the mean concentrations of chemicals occurring in U.S. public drinking water systems using fluoride and thallium as examples. The data used are Safe Drinking Water Act compliance monitoring data (with a significant proportion of left-censored data). The model, which assumes log-normality, was evaluated using simulated data sets generated from a series of Weibull distributions to illustrate the robustness of the model. The hierarchical model is easily implemented using the Markov chain Monte Carlo simulation method. In addition, the Bayesian method is able to quantify the uncertainty in the estimated cumulative density function. The estimated fluoride and thallium national distributions are presented. Results from this study can be used to develop prior distributions for future U.S. drinking water regulatory studies of contaminant occurrence.     

In situ observation of CO2 sequestration reactions using a novel microreaction system

A novel, externally controlled microreaction system has been developed to provide the first in situ observations of the reaction processes that control CO2 sequestration via mineral carbonation. The system offers pressure (to 20 MPa), temperature (to 250 degrees C), and activity control suitable for investigating a variety of fluid-fluid and fluid-solid interactions of environmental interest. Mineral sequestration efforts to date have effectively accelerated carbonation, a natural mineral weathering process, to an industrial timescale. However, the associated reaction mechanisms are poorly understood, limiting further process development. Synchrotron X-ray diffraction and Raman spectroscopy have been used to provide the first in situ insight into the associated supercritical mineral carbonation process. Magnesite was found to form directly under the reaction conditions observed (e.g., 150 degrees C and 15 MPa CO2),facilitating geologically stable sequestration. Thermodynamic analysis of fluid-phase species concentrations in the Na+ buffered H2O-CO2 reaction system found the primary aqueous reactant species to be CO2(aq) and HCO3-, with CO2(aq) more prevalent under the reaction conditions observed. The microreactor provides a powerful new tool for in situ investigation of a broad range of environmentally, fundamentally, and commercially important processes, including the reactions associated with geological carbon dioxide sequestration.