Characterisation of black carbon-rich samples by <Superscript>13</Superscript>C solid-state nuclear magnetic resonance

There are difficulties in quantifying and characterising the organic matter (OM) in soils that contain significant amounts of partially oxidised char or charcoal materials. The anthropogenic black carbon (BC), such as that found in the Terra Preta de índio soils of the Amazon region, is a good example of the OM that is difficult to analyse in such soils. ¹³C direct polarisation/magic angle spinning (DP/MAS) at high MAS frequency, ¹H-¹³C cross polarisation (CP)/MAS with total suppression of spinning sidebands (TOSS), and chemical shift anisotropy (CSA) filter nuclear magnetic resonance techniques have been applied successfully for quantifying the different components of OM. However, because pyrogenic materials present strong local magnetic susceptibility heterogeneities, the use of CSA-filter and TOSS make the pulse sequences very sensitive to imperfections in the π pulses. In this study, the DP/MAS pulse sequence was replaced by a CP with a radio frequency ramp—variable amplitude CP (VACP)—VACP/MAS pulse sequence, and composite π pulses were used in the CSA-filter and TOSS pulse sequences. In that way, the component functionalities in a humic acid from a BC soil were successfully determined. The spectrometer time needed was greatly decreased by employing this VACP/MAS technique. This development provides an accurate method for characterising BC-rich samples from different origins.     

Detection and analysis of xenon isotopes for the comprehensive nuclear-test-ban treaty international monitoring system

The use of the xenon isotopes for detection of nuclear explosions is of great interest for monitoring compliance with the comprehensive nuclear-test-ban treaty (CTBT). Recently, the automated radioxenon sampler-analyzer (ARSA) was tested at the Institute for Atmospheric Radioactivity (IAR) in Freiburg, Germany to ascertain its use for the CTBT by comparing its results to laboratory-based analyses, determining its detection sensitivity and analyzing its results in light of historical xenon isotope levels and known reactor operations in the area. Xe-133 was detected nearly every day throughout the test at activity concentrations ranging between approximately 0.1 mBq/m3 to as high as 120 mBq/m3. Xe-133m and 135Xe were also detected occasionally during the test at concentrations of less than 1 to a few mBq/m3.     

TNT particle size distributions from detonated 155-mm howitzer rounds

To achieve sustainable range management and avoid or minimize environmental contamination, the Army needs to know the amount of explosives deposited on ranges from different munitions and how these are degraded and transported under different geological and climatic conditions. The physical form of the deposited explosives has a bearing on this problem, yet the shapes and size distributions of the explosive particles remaining after detonations are not known. We collected residues from 8 high-order and 6 low-order non-tactical detonations of TNT-filled 155-mm rounds. We found significant variation in the amount of TNT scattered from the high-order detonations, ranging from 0.00001 to 2% of the TNT in the original shell. All low-order detonations scattered percent-level amounts of TNT. We imaged thousands of TNT particles and determined the size, mass and surface-area distributions of particles collected from one high-order and one low-order detonation. For the high-order detonation, particles smaller than 1 mm contribute most of the mass and surface area of the TNT scattered. For the low-order detonation, most of the scattered TNT mass was in the form of un-heated, centimeter-sized pieces whereas most of the surface area was again from particles smaller than 1 mm. We also observed that the large pieces of TNT disintegrate readily, giving rise to many smaller particles that can quickly dissolve. We suggest picking up the large pieces of TNT before they disintegrate to become point sources of contamination.     

Use of an indoor air quality model (IAQM) to estimate indoor ozone levels

Currently, outdoor ozone levels in many U.S. cities exceed the primary health-based national ambient air quality standard. While outdoor ozone levels are an important measure of the severity of those exceedances, people typically spend more than 80 percent of their time indoors, where ozone levels are lower. Indoor ozone levels range from 10 to 80 percent of outdoor levels, with many people receiving a substantial portion of their ozone exposure while indoors. This paper uses an indoor air quality model (IAQM) to estimate indoor ozone levels by microenvironment type (home, office, and vehicle) and configuration (windows open, windows closed, older construction, weatherized, and air conditioned). The formulation of IAQM is discussed, along with specification of model parameters for ozone. The multicompartment version of IAQM is described, with a single-compartment version used for the analyses. IAQM-calculated ozone indoor-outdoor ratios compare well with research-reported values. Results indicate that ozone peak-concentration indoor-outdoor ratios range as follows: home--0.65 (windows open), 0.36 (air conditioned), 0.23 (typical construction, windows closed), and 0.05 (energy-efficient construction, windows closed); office--0.82 (heating, ventilation and air conditioning systems supplying 100 percent outdoor air), 0.60 (typical HVAC), and 0.32 (energy-efficient HVAC); and vehicle--0.41 (85 mph), 0.33 (55 mph), and 0.21 (10 mph). Analysis results are presented to characterize IAQM's sensitivity to assumed model parameters.     

Nitrate and water supplies in the United Kingdom

Nitrate concentrations in UK waters are rising, with the highest levels occurring in the south and east of England, particularly Lincolnshire, Cambridgeshire and East Anglia. The source of the nitrate is arable agriculture where intensification in the last few decades has increased nitrate leaching from soils into both surface and underground waters. Concentrations in underground waters are expected to reach 150 to 200 mg litre(-1) nitrate (i.e. NO(3)) in the future, if agricultural losses remain stable. No widespread environmental deterioration due to nitrate has been observed in rivers or lakes. Excessive concentrations of nitrate in drinking waters can cause methaemoglobinaemia (blue-baby syndrome) in bottle-fed infants and the government Chief Medical Officer has recommended that a maximum concentration of 100 mg litre(-1) is appropriate for public water supplies in the UK. This level has not been exceeded in public water supplies in the UK, but maintaining it has cost approximately 15m pounds in borehole replacement and arrangements to blend high and low nitrate waters. Future capital costs are estimated as 37m pounds over the next 20 years. The European Economic Community (EEC) Drinking Water Directive (80/778/EEC) sets a maximum admissible concentration of 50 mg litre(-1) nitrate. Adherence to this standard will cost 199m pounds over the same period.     

Septic tank and agricultural non‐point source pollution within a rural watershed

This investigation addresses the problem of Non‐Point Source (NPS) pollution in the rural Lake Weatherford watershed in Parker County, Texas. This reservoir is the primary municipal water supply for the City of Weatherford, Texas. The principal method of wastewater disposal is the on‐site system or septic tanks for the small residential areas surrounding the reservoir.

Sources of NPS pollution of interest in this watershed include agricultural operations as well as the residential areas. These sites were identified with the aid of aerial photography and field investigation. Suspected NPS problems were substantiated through a sampling program involving chemical and biological testing of the reservoir. Results indicate that there is significant NPS pollution contamination of Lake Weatherford from agricultural sources and seepage from on‐site wastewater disposal systems. Excessive fecal coliform and fecal streptococcus counts (>500 bacteria/100 ml) were generally associated with rainfall events and several samples showed values > 100000 bacteria/100 ml. The fecal coliform/fecal streptococcus ratios indicated contamination from human sources, animal sources, and a combination of both. Nutrient concentrations fluctuated from quite low to high with ammonia as the most consistent problem. High ammonia values were also associated with rainfall events.     

Predicted uranium and radon concentrations in New Hampshire (USA) groundwater—Using Multi Order Hydrologic Position as predictors

Two radioactive elements, uranium (U) and radon (Rn), which are of potential concern in New Hampshire (NH) groundwater, are investigated. Exceedance probability maps are tools to highlight locations where the concentrations of undesirable substances in the groundwater may be elevated. Two forms of statistical analysis are used to create exceedance probability maps for U and Rn in NH groundwater. The first, Boosted Regression Tree (BRT), was selected for estimating U exceedance values. It computes exceedance values directly using the Bernoulli distribution function. The second method of statistical analysis used for Rn to determine exceedance probabilities is ordinary least squares (OLS) regression. In the process of determining exceedance probabilities for U and Rn, the utility of a new dataset is investigated. That new predictor dataset is the Multi-Order Hydrologic Position (MOHP) dataset. MOHP raster datasets have been produced nationally for the conterminous United States at a 30-m resolution. The concept behind MOHP is that, for any given point on the earth's surface, there is the potential for a longer groundwater flow path as one goes deeper beneath the land surface. MOHP predictors were tested in both models. Three MOHP predictors were found useful in the BRT model and two in the OLS model. MOHP data were found useful as predictors along with other site characteristics in predicting U and Rn exceedance probabilities in New Hampshire groundwater.     

Analysis of munitions constituents in groundwater using a field-portable GC-MS

The use of munitions constituents (MCs) at military installations can produce soil and groundwater contamination that requires periodic monitoring even after training or manufacturing activities have ceased. Traditional groundwater monitoring methods require large volumes of aqueous samples (e.g., 2-4 L) to be shipped under chain of custody, to fixed laboratories for analysis. The samples must also be packed on ice and shielded from light to minimize degradation that may occur during transport and storage. The laboratory’s turn-around time for sample analysis and reporting can be as long as 45 d. This process hinders the reporting of data to customers in a timely manner; yields data that are not necessarily representative of current site conditions owing to the lag time between sample collection and reporting; and incurs significant shipping costs for samples.The current work compares a field portable Gas Chromatograph-Mass Spectrometer (GC-MS) for analysis of MCs on-site with traditional laboratory-based analysis using High Performance Liquid Chromatography with UV absorption detection. The field method provides near real-time (within ∼1 h of sampling) concentrations of MCs in groundwater samples. Mass spectrometry provides reliable confirmation of MCs and a means to identify unknown compounds that are potential false positives for methods with UV and other non-selective detectors.