Application of a compact all solid-state laser system to the in situ detection of atmospheric OH,HO2, NO and IO by laser-induced fluorescence

A tuneable, high pulse-repetition-frequency, solid state Nd:YAG pumped titanium sapphire laser capable of generating radiation for the detection of OH, HO2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF) has been developed. The integration of the laser system operating at 308 nm into a field measurement apparatus for the simultaneous detection of hydroxyl and hydroperoxy radicals is described, with detection limits of 3.1 x 10(5) molecule cm(-3) (0.012 pptv in the boundary layer) and 2.6 x 10(6) molecule cm(-3) (0.09 pptv) achieved for OH and HO2 respectively (30 s signal integration, 30 s background integration, signal-to-noise ratio = 1). The system has been field tested and offers several advantages over copper vapour laser pumped dye laser systems for the detection of atmospheric OH and HO2 radicals by LIF, with benefits of greater tuning range and ease of use coupled with reduced power consumption, instrument footprint and warm-up time. NO has been detected in the atmosphere at approximately 1 ppbv by single photon LIF using the Alpha 2Sigma+ <-- Chi 2Pi1/2 (0,0) transition at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a chemiluminescence analyser. With some improvements in performance, particularly with regard to laser power, the theoretical detection limit for NO is projected to be approximately 2 x 10(6) molecule cm(-3) (0.08 pptv). Whilst operating at 445 nm, the laser system has been used to readily detect the IO radical in the laboratory, and although it is difficult to project the sensitivity in the field, an estimate of the detection limit is < 1 x 10(5) molecule cm(-3) (< 0.004 pptv), well below previously measured atmospheric concentrations of IO.     

Contaminant exposure of willets feeding in agricultural drainages of the Lower Rio Grande Valley of South Texas

Willets (Catoptrophorus semipalmatus) were collected in June and August 1986 at the outlets of two agricultural drainages into the Lower Laguna Madre of South Texas and at two other Texas coastal sites. Mean liver concentration of arsenic was higher in August than June. Over 20% of the livers had arsenic concentrations elevated above a suggested background level of 5.0 ppm dry weight (DW), but concentrations (maximum 15 ppm) were below those associated with acute toxicity. Selenium concentration in livers varied from 2.3 to 8.3 ppm DW for all locations and represented background levels. Mercury concentrations in livers for all locations (means = 2.0 to 3.4, maximum 17 ppm DW) were below those associated with avian mortality and similar to levels found in other estuarine/marine birds. DDE in carcasses was higher in adults (mean = 1.0 ppm wet weight) than juveniles (0.2 ppm), and higher in August (1.0 ppm) than June (0.5 ppm); however, DDE concentrations were generally at background levels. Based on brain cholinesterase activity, willets were not recently exposed to organophosphate pesticides.     

Post-remediation evaluation of a LNAPL site using electrical resistivity imaging

Present understanding of the earth's subsurface is most often derived from samples at discrete points (wells) and interpolations or models that interpret the space between these points. Electrical resistivity imaging techniques have produced an improved capability to map contaminants (especially NAPLs--NonAqueous Phase Liquids) away from traditional wells using actual field data. Electrical resistivity image data, confirmed by drilling, have demonstrated that LNAPL (Light NAPL--less dense than water, such as gasoline) contaminants exist outside of a delineated and remediated area in Golden, Oklahoma. The data also demonstrate that LNAPL exists between monitoring and remediation wells which indicate low contaminant levels when sampled. Additionally, the electrical images provided the drilling location with the highest concentration of hydrocarbon ever found on the site, even after two phases of remediation work had been performed, although the sampling protocols varied. The results indicate that current methods of post-remediation site characterization are inadequate for complete site characterization.     

Effective application of monitoring information: the case of San Francisco Bay

The San Francisco Estuary Regional Monitoring Program (RMP) for Trace Substances is an innovative partnership among a regulatory agency, more than 70 regulated entities, and an independent scientific organization. The institutional arrangement behind the RMP has made the regulatory system increasingly responsive to emerging management needs, particularly with regard to the development of total maximum daily loads and ecosystem impairment assessment. Through multi-agency partnerships within and outside the RMP institutional structure, major information gaps for several pollutants of concern have been narrowed, resulting in a successful consensus-based regulatory approach to managing copper and nickel mass inputs into the Estuary. Short-term research efforts, based upon monitoring results, helped identify the most cost-effective control and remediation options for various bioaccumulative substances. Additionally, adaptive changes to the monitoring program documented the existence of widespread aquatic toxicity in the Estuary that is apparently due to pesticide runoff from agricultural and urban areas. One of the most important contributions of this collaborative monitoring program is the deliberate and systematic adjustment of management and research questions that serve to influence and add relevance to the overall research agenda related to San Francisco Estuary ecosystem assessment.     

Establishing the link between ammonia emission control and measurements of reduced nitrogen concentrations and deposition

In the context of international efforts to reduce the impactsof atmospheric NH₃ and NH₄ ⁺ (collectively, NH_x), it is important to establish the link between NH₃emissions and monitoring of NH_x concentrations and deposition. This is equally relevant to situations where NH₃emissions changes are certain (e.g. due to changed source sectoractivity), as to cases where NH₃ abatement technologies havebeen implemented. Correct interpretation of adequate atmosphericmeasurements is essential, since monitoring data provide the onlymeans to evaluate trends in regional NH₃ emissions.These issues have been reviewed using available measurements and modelling from nine countries. In addition to historic datasets,the analysis here considers countries where NH₃ source sector activity changed (both increases and decreases) and countries where NH₃ abatement policies have been implemented.In The Netherlands an `ammonia gap' was identified between the expected reduction and results of monitoring, and was attributedinitially to ineffectiveness of the abatement measures. The analysis here for a range of countries shows that atmospheric interactions complicate the expected changes, particularly sinceSO₂ emissions have decreased at the same time, while at manysites the few years of available data show substantial inter-annual variation. It is concluded that networks need to beestablished that speciate between NH₃ and aerosol NH₄ ⁺, in addition to providing wet deposition, and sample at sufficient sites for robust regional estimates to be established. Such measurements will be essential to monitor compliance of the international agreements on NH₃ emission abatement.     

RCRA ground-water monitoring decision procedures viewed as quality control schemes

The problems of developing and comparing statistical procedures appropriate to the monitoring of ground water at hazardous waste sites are discussed. It is suggested that these decision procedures should be viewed as quality control schemes and compared in the same way that industrial quality control schemes are compared. The results of a Monte Carlo simulation study of run-length distribution of a combined Shewhart-CUSUM quality control scheme are reported.     

Optimizing the removal of carbon phases in soils and sediments for sequential chemical extractions by coulometry

We have developed a coulometric technique to optimize the removal of the carbonate and organic fractions for sequential chemical extractions of soils and sediments. The coulometric system facilitates optimizing these two fractions by direct real-time measurement of carbon dioxide (CO2) evolved during the removal of these two fractions. Further analyses by ICP-MS and alpha-spectrometry aided in interpreting the results of coulometry experiments. The effects of time, temperature, ionic strength and pH were investigated. The sensitivity of the coulometric reaction vessel/detection system was sufficient even at very low total carbon content (< 0.1 mol kg-1). The efficiency of the system is estimated to be 96% with a standard deviation of 8%. Experiments were carried out using NIST Standard Reference Materials 4357 Ocean Sediment (OS), 2704 Buffalo River Sediment (BRS), and pure calcium carbonate. Carbonate minerals were dissolved selectively using an ammonium acetate-acetic acid buffer. Organic matter was then oxidized to CO2 using hydrogen peroxide (H2O2) in nitric acid. The carbonate fraction was completely dissolved within 120 min under all conditions examined (literature suggests up to 8 h). For the OS standard, the oxidation of organic matter self-perpetuates between 45 and 50 degrees C, a factor of two less than commonly suggested, while organic carbon in the BRS standard required 80 degrees C for the reaction to proceed to completion. For complete oxidation of organic matter, we find that at least three additions of H2O2 are required (popular methods suggest one or two).     

International CO2 emissions targets and timetables: An analysis of the AOSIS proposal

In this paper, we use a two-region version of the CETA model to analyze international CO₂ emission control policies. The policies we consider are all substantially equivalent to a policy recently proposed by the Alliance of Small Island States (AOSIS). The AOSIS proposal requires the OECD alone to reduce emissions, while the alternatives we consider achieve equivalent reductions via emission rights traded (1) between regions, (2) between time periods, or (3) both. We find that tradeable rights systems provide significant overall cost savings relative to the AOSIS proposal. Cost reductions may be roughly 60% for rights tradeable between regions, 50% for rights tradeable between time periods, and 95% for rights tradeable between regions and time periods. The benefits of these cost reductions accrue to both the OECD and the Rest of the World. Our results underscore the importance of using an efficient policy to achieve any given atmospheric concentration objective.