Mobility control: How injected surfactants and biostimulants may be forced into low‐permeability units

Recovering dense nonaqueous‐phase liquid (DNAPL) remains one of the most difficult problems facing the remediation industry. Still, the most common method of recovering DNAPL is to physically remove the contaminants using common technologies such as total fluids recovery pumps, vacuum systems, and “pump‐and‐treat.” Increased DNAPL removal can be attained using surfactants to mobilize and/or solubilize the pollutants. However, very little is understood of the methods developed by petroleum engineers beginning in the 1960s to overcome by‐passed, low‐permeability zones in heterogeneous oil reservoirs. By injecting or causing the formation of viscous fluids in the subsurface, petroleum engineers caused increased in‐situ pressures that forced fluid flow into low permeability units as well as the higher permeability thief zones. Polymer flooding involves injecting a viscous aqueous polymer solution into the contaminated aquifer. Foam flooding involves injecting surfactant to decontaminate the high‐permeability zones and then periodic pulses of air to cause a temporary viscous foam to form in the high‐permeable zones after all DNAPL is removed. Later surfactant pulses are directed by the foam into unswept low‐permeable units. These methods have been applied to DNAPL removal using surfactants but they can also be applied to the injection of bio‐amendments into low‐permeability zones still requiring continued remediation. Here we discuss the principles of mobility control as practiced in an alluvial aquifer contaminated with chlorinated solvent and coal tar DNAPLs as well as some field results. © 2003 Wiley Periodicals, Inc.     

Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.     

Hot Spots of Perforated Forest in the Eastern United States

National assessments of forest fragmentation satisfy international biodiversity conventions, but they do not identify specific places where ecological impacts are likely. In this article, we identify geographic concentrations (hot spots) of forest located near holes in otherwise intact forest canopies (perforated forest) in the eastern United States, and we describe the proximate causes in terms of the nonforest land-cover types contained in those hot spots. Perforated forest, defined as a 0.09-ha unit of forest that is located at the center of a 7.29-ha neighborhood containing 60–99% forest with relatively low connectivity, was mapped over the eastern United States by using land-cover maps with roads superimposed. Statistically significant (P < 0.001) hot spots of high perforation rate (perforated area per unit area of forest) were then located by using a spatial scan statistic. Hot spots were widely distributed and covered 20.4% of the total area of the 10 ecological provinces examined, but 50.1% of the total hot-spot area was concentrated in only two provinces. In the central part of the study area, more than 90% of the forest edge in hot spots was attributed to anthropogenic land-cover types, whereas in the northern and southern parts it was more often associated with seminatural land cover such as herbaceous wetlands.     

Alfalfa rapidly remediates excess inorganic nitrogen at a fertilizer spill site

By 19%, standard remediation techniques had significantly reduced the concentration of nitrate nitrogen (NO3- -N) in local ground water at the site of a 1989 anhydrous ammonia spill, but NO3- -N concentrations in portions of the site still exceeded the public drinking water standard. Our objective was to determine whether local soil and ground water quality could be improved with alfalfa (Medicago sativa L.). A 3-yr study was conducted in replicated plots (24 by 30 m) located hydrologically upgradient of the ground water under the spill site. Three alfalfa entries ['Agate', Ineffective Agate (a non-N2-fixing elite germplasm similar to Agate), and MWNC-4 (an experimental germplasm)] were seeded in the spring of 1996. Corn (Zea mays L.) or wheat (Triticum aestivum L.) was seeded adjacent to the alfalfa each year. Crops were irrigated with N-containing ground water to meet water demand. During the 3-yr period, about 540 kg of inorganic N was removed from the aquifer through irrigation of 4.9 million L water. Cumulative N removal from the site over 3 yr was 972 kg N ha(-1) in Ineffective Agate alfalfa hay, compared with 287 kg N ha(-1) for the annual cereal grain. Soil solution NO3- concentrations were reduced to low and stable levels by alfalfa, but were more variable under the annual crops. Ground water quality improved, as evidenced by irrigation water N concentration. We do not know how much N was removed by the N2-fixing alfalfas, but it appears that either fixing or non-N2-fixing alfalfa will effectively remove inorganic N from N-affected sites.     

Modeling Parent and Metabolite Fate and Transport in Subsurface Drained Fields With Directly Connected Macropores1

Abstract: Few studies exist that evaluate or apply pesticide transport models based on measured parent and metabolite concentrations in fields with subsurface drainage. Furthermore, recent research suggests pesticide transport through exceedingly efficient direct connections, which occur when macropores are hydrologically connected to subsurface drains, but this connectivity has been simulated at only one field site in Allen County, Indiana. This research evaluates the Root Zone Water Quality Model (RZWQM) in simulating the transport of a parent compound and its metabolite at two subsurface drained field sites. Previous research used one of the field sites to test the original modification of the RZWQM to simulate directly connected macropores for bromide and the parent compound, but not for the metabolite. This research will evaluate RZWQM for parent/metabolite transformation and transport at this first field site, along with evaluating the model at an additional field site to evaluate whether the parameters for direct connectivity are transferable and whether model performance is consistent for the two field sites with unique soil, hydrologic, and environmental conditions. Isoxaflutole, the active ingredient in BALANCE^® herbicide, was applied to both fields. Isoxaflutole rapidly degrades into a metabolite (RPA 202248). This research used calibrated RZWQM models for each field based on observed subsurface drain flow and/or edge of field conservative tracer concentrations in subsurface flow. The calibrated models for both field sites required a portion (approximately 2% but this fraction may require calibration) of the available water and chemical in macropore flow to be routed directly into the subsurface drains to simulate peak concentrations in edge of field subsurface drain flow shortly after chemical applications. Confirming the results from the first field site, the existing modification for directly connected macropores continually failed to predict pesticide concentrations on the recession limbs of drainage hydrographs, suggesting that the current strategy only partially accounts for direct connectivity. Thirty‐year distributions of annual mass (drainage) loss of parent and metabolite in terms of percent of isoxaflutole applied suggested annual simulated percent losses of parent and metabolite (3.04 and 1.31%) no greater in drainage than losses in runoff on nondrained fields as reported in the literature.     

ENHANCEMENTS OF NONPOINT SOURCE MONITORING OF VOLATILE ORGANIC COMPOUNDS IN GROUND WATER1

ABSTRACT: The U.S. Geological Survey (USGS) has compiled a national retrospective data set of analyses of volatile organic compounds (VOCs) in ground water of the United States. The data are from Federal, State, and local nonpoint‐source monitoring programs, collected between 1985–95. This data set is being used to augment data collected by the USGS National Water‐Quality Assessment (NAWQA) Program to ascertain the occurrence of VOCs in ground water nationwide. Eleven attributes of the retrospective data set were evaluated to determine the suitability of the data to augment NAWQA data in answering occurrence questions of varying complexity. These 11 attributes are the VOC analyte list and the associated reporting levels for each VOC, well type, well‐casing material, type of openings in the interval (screened interval or open hole), well depth, depth to the top and bottom of the open interval(s), depth to water level in the well, aquifer type (confined or unconfined), and aquifer lithology. VOCs frequently analyzed included solvents, industrial reagents, and refrigerants, but other VOCs of current interest were not frequently analyzed. About 70 percent of the sampled wells have the type of well documented in the data set, and about 74 percent have well depth documented. However, the data set generally lacks documentation of other characteristics, such as well‐casing material, information about the screened or open interval(s), depth to water level in the well, and aquifer type and lithology. For example, only about 20 percent of the wells include information on depth to water level in the well and only about 14 percent of the wells include information about aquifer type. The three most important enhancements to VOC data collected in nonpoint‐source monitoring programs for use in a national assessment of VOC occurrence in ground water would be an expanded VOC analyte list, recording the reporting level for each analyte for every analysis, and recording key ancillary information about each well. These enhancements would greatly increase the usefulness of VOC data in addressing complex occurrence questions, such as those that seek to explain the reasons for VOC occurrence and nonoccurrence in ground water of the United States.     

REMOVAL OF FLOODWATER SEDIMENTS BY A CLEARCUT TUPELO-CYPRESS WETLAND1

ABSTRACT: A palustrine water tupelo (Nyssa aquatica L.)-baldcy-press (Taxodium distichum (L.) Rich.) swamp in southwestern Alabama was subjected to three types of disturbance, including helicopter logging, rubber-tired skidder logging simulation, and helicopter logging followed by an herbicide application. An adjacent undisturbed stand served as a control area. Post-harvest collection of sedimentation data revealed that the herbaceous and woody vegetation regrowth within the helicopter and skidded clearcut areas trapped more sediments than did the control or herbicide treatment areas. Clearcutting, followed by plant regrowth, improved the wet-land's capacity to remove sediments from overbank flow flood waters.     

SUMMER LOW FLOWS IN NEW ENGLAND DURING THE 20TH CENTURY1

ABSTRACT: High springtime river flows came earlier by one to two weeks in large parts of northern New England during the 20th Century. In this study it was hypothesized that late spring/early summer recessional flows and late summer/early fall low flows could also be occurring earlier. This could result in a longer period of low flow recession and a decrease in the magnitude of low flows. To test this hypothesis, variations over time in the magnitude and timing of low flows were analyzed. To help understand the relation between low flows and climatic variables in New England, low flows were correlated with air temperatures and precipitation. Analysis of data from 23 rural, unregulated rivers across New England indicated little evidence of consistent changes in the timing or magnitude of late summer/early fall low flows during the 20th Century. The interannual variability in the timing and magnitude of the low flows in northern New England was explained much more by the interannual variability in precipitation than by the interannual variability of air temperatures. The highest correlation between the magnitude of the low flows and air temperatures was with May through November temperatures (r =?0.37, p= 0.0017), while the highest correlation with precipitation was with July through August precipitation (r = 0.67, p > 0.0001).     

Advanced solid-state carbon-13 nuclear magnetic resonance spectroscopic studies of sewage sludge organic matter: detection of organic "domains"

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.     

Using Sediment Budgets to Investigate the Pathogen Flux Through Catchments

We demonstrate a materials budget approach to identify the main source areas and fluxes of pathogens through a landscape by using the flux of fine sediments as a proxy for pathogens. Sediment budgets were created for three subcatchment tributaries of the Googong Reservoir in southeastern New South Wales, Australia. Major inputs, sources, stores, and transport zones were estimated using sediment sampling, dam trap efficiency measures, and radionuclide tracing. Particle size analyses were used to quantify the fine-sediment component of the total sediment flux, from which the pathogen flux was inferred by considering the differences between the mobility and transportation of fine sediments and pathogens. Gullies were identified as important sources of fine sediment, and therefore of pathogens, with the pathogen risk compounded when cattle shelter in them during wet periods. The results also indicate that the degree of landscape modification influences both sediment and pathogen mobilization. Farm dams, swampy meadows and glades along drainage paths lower the flux of fine sediment, and therefore pathogens, in this landscape during low-flow periods. However, high-rainfall and high-flow events are likely to transport most of the fine sediment, and therefore pathogen, flux from the Googong landscape to the reservoir. Materials budgets are a repeatable and comparatively low-cost method for investigating the pathogen flux through a landscape.