UV-VIS spectroscopy of 2,4,6-trinitrotoluene-hydroxide reaction

Contamination of groundwater, surface water and soil by explosives has occurred at military sites throughout the world as a result of manufacture of explosive compounds, assembly of munitions, and deployment of explosives containing devices. Due to the adverse effects of explosives on humans and other natural receptors, a low cost means of decontaminating these areas of contamination is needed. Base-induced transformation of explosives has shown promise as a rapid, low cost, and minimally resource-intensive technology for detoxifying explosives in soil and water. In order to understand the reaction mechanism, a reaction mixture of 2:1:1 (water:2,4,6-trinitrotoluene (TNT):1 N KOH) was analyzed by UV/VIS spectrometry from 190 to 1,100 nm. Time course measurements were conducted at 25, 20, 15, and 12 degrees C. A factor analysis program was used to analyze the spectral data. Principal component analysis indicated that six principal components explained the spectra to within experimental error, with four factors explaining the majority of the variance. Test spectral vectors for four components were developed, including TNT, two intermediates, and the final product, and were tested against the abstract vectors. Two possible reaction mechanisms were suggested and tested to explain the spectral data.     

Soil quality in New Zealand: policy and the science response

Soil depletion and degradation have been increasingly recognized as important environmental issues in many parts of the world. Over the last decade a number of political and legislative measures have been introduced to encourage and enforce sustainable soil management in New Zealand. Application of the new legislation has highlighted gaps in our knowledge of soil quality and a lack of scientific methods to assess and monitor soil quality. This paper describes the legislative measures and outlines the sdentific response to the needs of regulatory agencies responsible for maintaining environmental quality. The research recommended a set of indicators to assess soil quality. Each soil quality attribute has an associated "target range" defining the acceptable value for the attribute. The paper also discusses the communication of results to end-users, including the development of a computerized assessment tool. The legislative measures and scientific response have fostered a closer relationship between the policy and science communities, leading to more well-focused research, but greater collaboration is still required.     

Rhizosphere acidification and cadmium uptake by strawberry clover

Strawberry clover (Trifolium fragiferum L.) is a hardy legume found in indigenous or introduced populations throughout the world. Tolerance to saline and alkaline soils, flooding, and heavy metals make it a good prospect for reclamation projects. The research, described here, was conducted to: (i) characterize the morphological variation in plants from available seed sources, (ii) evaluate cadmium uptake and tolerances over a wide range of morphological variants, and (iii) elucidate the variability in the effects of roots on rhizosphere pH and the relationship to cadmium uptake. Seeds from selected accessions were planted in the greenhouse for comparison of morphological variation. The accessions examined had a mean height of 10.7+/-7 cm. Accessions 254916 and 237925 are tall with high rhizosphere pH values and might be useful in phytoremediation. Strawberry clover accessions were also grown hydroponically to examine differences in cadmium uptake. The ability of strawberry clover roots to change rhizosphere pH and take up cadmium was examined using culture tubes containing nutrient agar, a moderate level of cadmium, and a pH indicator dye. The results provided evidence for a negative correlation between rhizosphere pH and cadmium uptake.     

Real-time, high-resolution quantitative measurement of multiple soil gas emissions: selected ion flow tube mass spectrometry

A new technique is presented for the rapid, high-resolution identification and quantification of multiple trace gases above soils, at concentrations down to 0.01 microL L(-1) (10 ppb). The technique, selected ion flow tube mass spectrometry (SIFT-MS), utilizes chemical ionization reagent ions that react with trace gases but not with the major air components (N2, O2, Ar, CO2). This allows the real-time measurement of multiple trace gases without the need for preconcentration, trapping, or chromatographic separation. The technique is demonstrated by monitoring the emission of ammonia and nitric oxide, and the search for volatile organics, above containerized soil samples treated with synthetic cattle urine. In this model system, NH3 emissions peaked after 24 h at 2000 nmol m(-2) s(-1) and integrated to approximately 7% of the urea N applied, while NO emissions peaked about 25 d after urine addition at approximately 140 nmol m(-2) s(-1) and integrated to approximately 10% of the applied urea N. The monitoring of organics along with NH3 and NO was demonstrated in soils treated with synthetic urine, pyridine, and dimethylamine. No emission of volatile nitrogen organics from the urine treatments was observed at levels >0.01% of the applied nitrogen. The SIFT method allows the simultaneous in situ measurement of multiple gas components with a high spatial resolution of < 10 cm and time resolution <20 s. These capabilities allow, for example, identification of emission hotspots, and measurement of localized and rapid variations above agricultural and contaminated soils, as well as integrated emissions over longer periods.     

Stray field nuclear magnetic resonance of soil water: development of a new, large probe and preliminary results

Development, characterization, and preliminary results of a recent technique capable of local measurements of pore-size distribution by a spatially resolved low resolution nuclear magnetic resonance (NMR) technique are described. Potential environmental uses include studying the change in pore-size distribution caused by surface compaction, which influences surface runoff, and obtaining information on the physical state of non-aqueous compounds in porous materials, which should aid the selection of appropriate soil remediation methods. Stray field (STRAFI) imaging is an NMR technique that allows distortion-free imaging of materials with short NMR relaxation times. The sample is placed in the strong axial fringe field gradient of a superconducting NMR magnet. We report on a new, unique, large 5-cm-diameter STRAFI probe, and its use for three preliminary test cases: water in ceramics of known pore size, paraffin wax and oil in sandstone rock, and water in soil at different matric potentials. The imaging is confined to one dimension with a spatial resolution of the order of 100 microm for protons. The optimum position for imaging occurs at 2.62 T and a gradient of 12.1 T/m. Water relaxation decay curves can be measured at any position in the 8-cm-long sample. These curves are decomposed into a series of terms each corresponding to a different pore size. Preliminary results show continuum fits to decay curves for a soil drained to three different matric potentials. Such information will be useful for interpreting water retention curves and will lead to understanding of the behavior of fluids in the vadose zone.     

Soil and litter phosphorus-31 nuclear magnetic resonance spectroscopy: extractants, metals, and phosphorus relaxation times

Phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy is an excellent tool with which to study soil organic P, allowing quantitative, comparative analysis of P forms. However, for 31P NMR to be tative, all peaks must be completely visible, and in their correct relative proportions. There must be no line broadening, and adequate delay times must be used to avoid saturation of peaks. The objective of this study was to examine the effects of extractants on delay times and peak saturation. Two samples (a forest litter and a mineral soil sample) and three extractants (0.25 M NaOH, NaOH plus Chelex (Bio-Rad Laboratories, Hercules, CA), and NaOH plus EDTA) were used to determine the differences in the concentration of P and cations solubilized by each extractant, and to measure spin-lattice (T1) relaxation times of P peaks in each extract. For both soil and litter, NaOH-Chelex extracted the lowest concentrations of P. For the litter sample, T1 values were short for all extractants due to the high Fe concentration remaining after extraction. For the soil sample, there were noticeable differences among the extractants. The NaOH-Chelex sample had less Fe and Mn remaining in solution after extraction than the other extractants, and the longest delay times used in the study, 6.4 s, were not long enough for quantitative analysis. Delay times of 1.5 to 2 s for the NaOH and NaOH-EDTA were adequate. Line broadening was highest in the NaOH extracts, which had the highest concentration of Fe. On the basis of these results, recommendations for future analyses of soil and litter samples by solution 31P NMR spectroscopy include: careful selection of an extractant; measurement of paramagnetic ions extracted with P; use of appropriate delay times and the minimum number of scans; and measurement of T1 values whenever possible.     

Relationships between stream size,suspended particles,and filter-feeding macroinvertebrates in a great plains drainage network

Suspended fine particles (seston) are an important component of energy and nutrient cycling in streams, but they can also be pollutants. We examined seston dynamics and filter-feeding macroinvertebrate communities in sites representing headwaters to large rivers in the Kansas River drainage, northeastern KS. Seston samples were collected at least seasonally during low to moderate flows for one year beginning in the summer of 1999, and quality was assessed by determining organic content and C to N ratio. A rapid bioassessment approach was used to examine filter-feeders. Relationships between stream size and seston concentrations were markedly influenced by anthropogenic activities. There was no relationship between total seston concentration and stream size across all sites (r = 0.14, p > 0.05), but a significant, positive relationship was evident when impounded and suburban sites were excluded (r = 0.73, p < 0.01); this same trend was evident for organic and inorganic components. Seasonal patterns of C to N ratio were evident, with generally lower values during winter and highest values in summer. However, seasonal patterns were dampened in suburban sites and virtually absent below impoundments. Filter-feeder richness was correlated with average organic seston concentrations (r = 0.8, p < 0.01), but this relationship was also obscured by impoundments and suburban development. In particular, impoundments had a dramatic, negative effect on richness. Abundance of most hydropsychid caddisfly taxa was positively correlated with organic seston concentration. Results indicate there are significant patterns regarding seston, filter-feeders, and stream size in this Great Plains river system, but patterns are strongly influenced by human activities. These relationships are relevant to management issues regarding suspended particles and the potential development of bioassessment techniques.     

Phosphorus budgets and riverine phosphorus export in northwestern Ohio watersheds

Phosphorus (P) budgets for large watersheds are often used to predict trends in riverine P export. To test such predictions, we calculated annual P budgets for 1975-1995 for soils of the Maumee and Sandusky watersheds of northwestern Ohio and compared them with riverine P export from these watersheds. Phosphorus inputs to the soils include fertilizers, manure, rainfall, and sludge while outputs include crop removal and nonpoint-source export via rivers. Annual P inputs decreased due to reductions in fertilizer and manure inputs. Annual outputs increased due to increasing crop yields. Net P accumulation decreased from peak values of 13.4 and 9.5 kg P ha(-1) yr(-1) to 3.7 and 2.6 kg P ha(-1) yr(-1) for the Maumee and Sandusky watersheds, respectively. Thus, P budget analysis suggests that riverine P export should have increased throughout the study period, with smaller increases during more recent years. However, detailed water quality studies show that riverine export of total phosphorus (TP) has decreased by 25 to 40% and soluble reactive phosphorus (SRP) by 60 to 89%, both due primarily to decreases from nonpoint sources. We suggest that these decreases are associated with farmers' adoption of practices that minimize transport of recently applied P fertilizer and of sediments via surface runoff, coupled with changes in winter weather conditions. In comparison with most Midwestern watersheds, rivers draining these watersheds have high unit area yields of TP, low unit area yields of SRP, and high ratios of nonpoint source- to point source-derived P.     

The Lake Erie Agricultural Systems for Environmental Quality project: an introduction

In the last part of the twentieth century, recognition became widespread of the important effect of agricultural runoff on the health of aquatic ecosystems in the Lake Erie basin and elsewhere. Because of the efforts to remediate Lake Erie, the "dead lake" among the Laurentian Great Lakes, a number of research and demonstration projects were undertaken in the Lake Erie basin to evaluate and foster adoption of conservation tillage and other farming techniques that would reduce runoff while maintaining productivity. In addition, intensive water quality studies of long duration were begun on major tributaries to Lake Erie during this time. The Lake Erie Agricultural Systems for Environmental Quality (LEASEQ) project examined governmental programs, changes in agriculture, and changes in water and soil quality during the period 1975-1995, and sought to evaluate the linkages among these factors. The study area is characterized by extensive agricultural land use of soils developed from glacial materials deposited on Paleozoic sedimentary bedrock, mostly limestone. Tile drainage is extensive, particularly in slow-draining clay-rich lacustrine soils in the lower reaches of the watersheds. This paper introduces the study area, its geology, geography, soils, and agricultural history. In addition, we provide an overview of the LEASEQ concept and introduce the 11 other papers in this series, which provide a detailed exposition of the results of our studies.     

Copper and zinc speciation in the solution of a soil-sludge mixture

Only a small fraction of the transition metals content in sludge-amended soils is soluble, and yet this fraction is a major contributor to the mobility and bioavailability of the metals. The chemical species of zinc (Zn) and copper (Cu) in the soluble fractions of soil-sludge mixtures were characterized with respect to their charge, molecular weight, and stoichiometry using ion exchange resin and gel chromatography procedures. The change in the metals' species with time after sludge application was followed for 100 d. Copper in the water extracts of the sludge-sand mixtures was found almost exclusively in low molecular weight (below 1000 Da) complexes. Higher molecular weight (around 2500 Da) dissolved organic carbon (DOC) was present in the extracts as well, but this DOC fraction exhibited little complexation. Copper was present in the extracts mainly as negatively charged species throughout the incubation period, and zinc tended to form zwitter ions. As incubation progressed, the relative content of positively charged Zn in solution increased. Complexation capacity of DOC in sludge water extract, extrapolated to infinite dilution, was 8.75 mM Ca g(-1) DOC. When the complexation capacity of the extract is near saturation, a mean Cu-DOC complex can be defined. It consists of 1.9 Cu atoms attached to DOC species containing 5.6 C atoms. Thus, the organic Cu complexes consist primarily of about two Cu ions attached to DOC species containing only five or six C atoms. Amino acids and small peptides or polycarboxylic acids, such as citric acid, thus may be important complexing agents of the metal.