Water quality trading: credit stacking and ancillary benefits

Ecosystems can provide many services. Wetlands, for example, can help mitigate water pollution from point sources as well as non-point sources, serve as habitat for wildlife, sequester carbon and serve as a place for recreation. Studies have found that these services can have substantial value to society. The sale of ecosystem credits has been found to be a possible way to finance construction investments in wetlands and easements to farmers to take their land out of production. At the same time, selling one ecosystem service credit may not always be enough to justify the investment. Traditionally market participants have only been allowed to sell a single credit from one piece of land, but recently there have been discussions about the possibility of selling more than one credit from a piece of land because it potentially could lead to more efficient ecosystem service provision. Selling multiple credits is sometimes referred to as credit stacking. This paper is an empirical study of the potential for credit stacking applied to the services provided by wetlands in the Upper Mississippi River Basin, specifically nitrogen, phosphorus and wildlife credits. In the setting of our study where costs are discrete rather than continuous we found that wetlands are a cost-effective way to reduce the nitrogen loads from wastewater treatment plants and that stacking nitrogen, phosphorus and wildlife credits may improve social welfare while leading to a higher level of ecosystem services. However, for credit stacking to be welfare improving we found that there needs to be a substantial demand for the credit that covers the majority of the investment in wetlands, while the credit aggregator has a choice between what ecosystem projects to undertake. If the credit that covers the majority of investment is sold first and is the sole basis of the investment decision and the objective is to improve welfare, a sequential implementation of ecosystem credits is not recommended; it would not lead to an increase in the total amount of ecosystem services provided though it would increase profit for the credit producer.

Improving the stability of an oxime based electrochemical microsensor for organo-phosphate vapor detection

A micro gas sensor has been developed by our group for the detection of organo-phosphate vapors using an aqueous oxime solution. The analyte diffuses from the high flow rate gas stream through a porous membrane to the low flow rate aqueous phase. It reacts with the oxime PBO (1-Phenyl-1,2,3,-butanetrione 2-oxime) to produce cyanide ions, which are then detected electrochemically from the change in solution potential. Previous work on this oxime based electrochemistry indicated that the optimal buffer pH for the aqueous solution was approximately 10. A basic environment is needed for the oxime anion to form and the detection reaction to take place. At this specific pH, the potential response of the sensor to an analyte (such as acetic anhydride) is maximized. However, sensor response slowly decreases as the aqueous oxime solution ages, by as much as 80% in first 24 hours. The decrease in sensor response is due to cyanide which is produced during the oxime degradation process, as evidenced by the cyanide selective electrode. Solid phase micro-extraction carried out on the oxime solution found several other possible degradation products, including acetic acid, N-hydroxy benzamide, benzoic acid, benzoyl cyanide, 1-Phenyl 1,3-butadione, 2-isonitrosoacetophenone and an imine derived from the oxime. It was concluded that degradation occurred through nucleophilic attack by a hydroxide or oxime anion to produce cyanide, as well as a nitrogen atom rearrangement similar to Beckmann rearrangement. The stability of the oxime in organic solvents is most likely due to the lack of water, and specifically hydroxide ions. The reaction between oxime and organo-phosphate to produce cyanide ions requires hydroxide ions, and therefore pure organic solvents are not compatible with the current micro-sensor electrochemistry. By combining a concentrated organic oxime solution with the basic aqueous buffer just prior to being used in the detection process, oxime degradation can be avoided while preserving the original electrochemical detection scheme. Based on beaker cell experiments with selective cyanide sensitive electrodes, ethanol was chosen as the best organic solvent due to its stabilizing effect on the oxime, minimal interference with the aqueous electrochemistry, and compatibility with the current microsensor material (PMMA). Further studies showed that ethanol had a small effect on micro-sensor performance by reducing the rate of cyanide production and decreasing the overall response time. To avoid incomplete mixing of the aqueous and organic solutions, they were pre-mixed externally at a 10:1 ratio, respectively. To adapt the microsensor design to allow for mixing to take place within the device, a small serpentine channel component was fabricated with the same dimensions and material as the original sensor. This allowed for seamless integration of the microsensor with the serpentine mixing channel. Mixing in the serpentine microchannel takes place via diffusion. Both detector potential response and diffusional mixing improve with increased liquid residence time, and thus decreased liquid flowrate. Micromixer performance was studies at a 10:1 aqueous buffer to organic solution flow rate ratio, for a total rate of 5.5 μL/min. It was found that the sensor response utilizing the integrated micromixer was nearly identical to the response when the solutions were premixed and fed at the same rate.