Pesticide and Trace Metal Concentrations in Queensland Estuarine Crabs

Trace metals, metalloids and pesticide content were quantified in intertidal burrowing crabs Australoplax tridentata and a portunid Scylla serrata sampled from estuaries on the east coast of Australia between Cairns and Brisbane. Residues of dieldrin occurred at all locations, heptachlor epoxide and DDT (principally metabolites DDD and DDE) at most, reflecting historical use. Chlordane, chlorpyrifos and endosulfan were only detected in crabs in the urban Brisbane area, and neither hexachlorobenzene (HCB) or polychlorinated biphenyls (PCBs) were quantifiable. Calculations of ambient exposures to organochlorines based on residues in crab tissues indicated that dieldrin exceeded national water quality guidelines for protection of aquatic ecosystems at all sampling locations, but exposure to DDT and its metabolites was below the threshold of concern. Concentrations of trace metals and metalloids generally reflected sediment data and likely sources.     

Ground Water Sampling Bias Observed in Shallow, Conventional Wells

A previous field demonstration project on nitrate-based bioremediation of a fuel-contaminated aquifer used short-screened clustered well points in addition to shallow (10 foot), conventional monitoring wells to monitor the progress of remediation during surface application of recharge. These well systems were placed in the center and at one edge of each of two treatment cells. One cell received recharge amended with nitrate (nitrate cell), and the other received unamended recharge (control cell). Data from the clustered well points were averaged to provide a mean estimate for comparison with the associated conventional monitoring well.
Conservative tracer profiles were similar for each of the four systems, with better fits obtained for well systems located at the edge of the treatment cells. However, aromatic hydrocarbon and electron acceptor profiles varied greatly for the two center well systems, with the conventional monitoring well data suggesting that remediation was proceeding at a much more rapid rate than indicated by the cluster well points. Later tests with an electromagnetic borehole flowmeter demonstrated a significant vertical flow through the well-bore of the conventional monitoring well under simulated operating conditions. This created an artifact during sampling, thought to arise from preferential flow of recharge water from the water table to deeper portions of the contaminated zone resulting in several effects, including an actual decreased residence time of water sampled by the conventional well. These data provide additional evidence that conventional monitoring wells may be inadequate for monitoring remediation in the presence of significant vertical hydraulic gradients, even for fairly shallow homogeneous aquifers.     

Shallow Seismic Refraction Survey of Near-Surface Ground Water Flow

A shallow seismic refraction survey was conducted as part of a geologic and hydrologic investigation of an area adjacent to a proposed coal strip mine in southeastern Illinois. Data obtained from the survey were used to estimate the thickness and geometry of litho-logic units within approximately 40 feet of the surface in unconsolidated material overlying bedrock. Data from a nearby ground water monitoring well and several shallow geologic cores obtained in the survey area indicated the presence of a silt-clay unit roughly 10 feet beneath the surface. This unit strongly inhibits the vertical movement of ground water, resulting in a perched water table.
The refraction survey revealed that the morphology of the top of this silt-clay layer is dominated by a narrow, sinuous channel criss-crossing the survey region with an overall downward trend in elevation from the mine site to a small creek roughly 0.25 miles away. Detailed knowledge of the location of this channel was used to identify optimal sites for shallow ground water monitoring stations. The method proved to be a relatively rapid and cost-efficient means of obtaining detailed information concerning the thickness and geometry of the near-surface unconsolidated materials.     

Evidence for Enhanced Mineral Dissolution in Organic Acid-Rich Shallow Ground Water

Total concentrations of formate, acetate, and isobutyrate varied from less than 5 to greater than 9,000 μmol/l over distances of < 3 m in ground water from a shallow hydrocarbon contaminated aquifer. Laboratory incubations of aquifer material indicate that organic acid concentrations were dependent on the amount of hydrocarbon loading in the sediment and the relative rates of microbial organic acid production and consumption. In heavily contaminated sediments, production greatly exceeded consumption and organic acid concentrations increased. In lightly contaminated sediments rates were essentially equal and organic acid concentrations remained low. Concentrations of dissolved calcium, magnesium, and iron generally were one to two orders of magnitude higher in organic acid-rich ground water than in ground water having low organic acid concentrations. Carbonate and Fe(III)-oxyhydroxide minerals were the likely sources of these elements. Similarly, concentrations of dissolved silica, derived from quartz and k-feldspar, were higher in organic acid-rich ground water than in other waters. The positive relation (r = 0.60, p < .05, n = 16) between concentrations of silica and organic acids suggests that the microbially mediated buildup of organic acids in ground water enhanced quartz/k-feldspar dissolution in the aquifer, although it was not the only factor influencing their dissolution. A model that included organic acid microequivalents normalized by cation microequivalents significantly strengthened the correlation (r = 0.79, p < .001, n = 16) between dissolved silica and organic acid concentrations, indicating that competition between silica and cations for complexation sites on organic acids also influenced quartz/k-feldspar dissolution. Physical evidence for enhanced mineral dissolution in organic acid-rich waters included scanning electron microscopy images of highly corroded quartz and k-feldspar grains from portions of the aquifer containing organic acid-rich ground water. Microporosity generated in hydrocarbon contaminated sediments may adversely affect remediation efforts that depend on the efficient injection of electron acceptors into an aquifer or on the recovery of solutes from an aquifer.     

A Syringe and Cartridge Method for Down-Hole Sampling for Trace Organics in Ground Water

A newly developed technique which allows the down-hole sampling and subsequent analysis of ground water for trace organic contaminants was tested during an investigation of contaminant migration at an inactive landfill site in Burlington, Ontario, Canada. The sampling device, which is lowered down piezometers with a tube, consists of a small cylindrical cartridge of sorbent material attached to a syringe. Vacuum or pressure applied at the surface controls the movement of the plunger in the syringe. The volume of the syringe determines the volume of sample water that passes through the cartridge. The cartridge is removed from the syringe at the surface. One cartridge is used for each sampling; the syringe is reusable. The residual water in the cartridge is removed in the laboratory, and the cartridge is desorbed to a fused silica capillary column for analysis by gas chromatography (GC). The analyses discussed here were performed on a GC/mass spectrometer/data system (GC/MS/DS). Of the many organic compounds that were identified in the samples, three compounds were clearly landfill-related: 1,1,1-trichloroethane, chlorobenzene, and para-dichlorobenzene. The three compounds were found at levels substantially above blank levels in 9, 5, and 5 piezometers, respectively. The average concentrations were 14., 5.3, and 0.88μg/1 (ppb), respectively. The pooled coefficients of variation for the analyses for the three compounds were 27., 6.9, and 6.4%, respectively. The volatility of 1,1,1-trichloroethane was probably the cause of the greater variability in its analytical data. The main advantages of the technique over most conventional sampling methods include: (1) down-hole sampling in a manner which minimizes the potential for volatilization losses; (2) avoidance of passage of the sample through long sections of tubing that may contaminate the sample or cause adsorptive losses; (3) convenience of sample handling, storage, and shipping; and (4) high sensitivity.     

Hydrogen Peroxide Treatment of Septic Systems and Its Negative Effects on Shallow Ground Water

Soil-solution samplers and shallow ground water monitoring wells were utilized to monitor nitrate movement to ground water following H₂O₂ application to a clogged soil absorption system. Nitrate-nitrogen concentrations in soil water and shallow ground water ranged from 29 to 67 mg/L and 9 to 22 mg/L, respectively, prior to H₂O₂ treatment. Mean nitrate-nitrogen concentrations in soil water and ground water increased and ranged from 67 to 115 mg/L and 23 to 37 mg/L, respectively, one week after H₂O₂ application. Elevated concentrations of nitrate-nitrogen above background persisted for several weeks following H₂O₂ treatment. The H₂O₂ treatment was unsuccessful in restoring the infiltrative capacity of a well-structured soil. Application of H₂O₂ to the soil absorption system poses a threat of nitrate contamination of ground water and its usefulness should be fully evaluated before rehabilitation is attempted.     

Investigation of Possible Contamination of Shallow Ground Water by Deeply Injected Liquid Industrial Wastes

The objective of this study was to assess the possible impact of deep well disposal operations, conducted between 1958 and 1974, on the ground water quality in a shallow fresh water aquifer beneath Sarnia, Ontario, Canada. Because of the breakout of formation fluids in Sarnia and Port Huron, Michigan, in the early 1970s, it had been hypothesized that liquid waste from the disposal zone in bedrock had leaked through numerous abandoned oil, gas, and salt wells in the area up to the shallow fresh water aquifer and from there to the surface.
A monitoring well network of 29 5cm (2 inch) diameter piezometers was established in the thin sand and shale aquifer system, which exists between 30 and 70m (100 and 230 feet) below ground surface. In addition, a 300m (1000 foot) deep borehole was drilled and instrumented with a Westbay multilevel casing, which permitted sampling of the disposal zone.
Ground water samples from the shallow monitoring wells and the Westbay multilevel casing were analyzed for volatiles by GC/MS. Those volatile aromatics that were conspicuously present in the deep disposal zone, e.g., ethyl toluenes and trimethyl benzene, were not detected in the shallow monitoring wells. Thus, if contaminants from the disposal zone did indeed migrate to the shallow aquifer, contamination was not widespread and probably consisted mostly of displaced chloride-rich formation waters.     

A Field Test of Electromigration as a Method for Remediating Sulfate from Shallow Ground Water

Eloctromigraiion offers a potential tool for remediating ground water contaminated with highly soluble components, such as Na⁺, Cl, NO₃ and SO₄⁻. A field experiment was designed to lest the efficacy of electromigration for preconcontrating dissolved SO₄² in ground water associated with a fossil-fuel power plant. Two shallow wells, 25 feel apart (one 25 feel deep, the other 47 feet deep), were constructed in the upper portion of an unconfined alluvial aquifer. The wells were constructed with a double-wall design, with an outer casing of 4-inch PVC and an inner lube of 2-inch FVC; both were fully slotted (0.01 inch). Electrodes were constructed by wrapping the inner lulling with a 100-foot length of rare-earth metal oxide/copper wire. An electrical potential of 10.65 volts DC Was applied, and tests were run for periods of 12, 44, and 216 hours. Results showed large changes in the pH from the initial pH of ground water of about 7.5 to values of approximately 2 and 12 at the anode and cathode, respectively. Despite the fact that the test conditions were far from ideal, dissolved SO₄^2-; was significantly concentrated at the anode. Over a period of approximately nine days, the concentration of SO₄^2- at the anode reached what appeared to he a steady-state value of 2200 mg/L. compared lo the initial value in ground water of approximately 1150 mg/L. The results of this field lest should encourage further investigation of electromigration as a tool in the remediation of contaminated ground water.     

Fluoride in Nebraska's Ground Water

Fluoride concentrations in ground water are generally low but play an important role in dental health. This study evaluates the vertical and spatial distribution of fluoride in Nebraska's ground water and examines the geological and geochemical processes that control its concentration. Data from 1794 domestic wells sampled by the Nebraska Department of Health and Human Services. Regulation, and Licensure (NDOH) had a range of fluoride concentrations from <0.1 to 2.6 mg/L. and a median concentration of 0.3 mg/L. The median fluoride concentrations for Nebraska's 13 ground water regions varied from 0.2 to 0.7 mg/L. In each of these regions, individual wells may have either insufficient or overabundant F concentrations; we recommend that individual private water systems be tested for fluoride. Based on these data, system-specific recommendations can be made regarding the necessity for fluoridation.
Geochemical data indicated that the majority of fluoride occurs as F. Dissolution of F-bearing minerals controls fluoride occurrence. Apatite plus minor amounts of fluorite along with significant ground water residence times are the primary factors controlling F in the water from the Dakota Formation in Knox County, as well as in other parts of northeastern Nebraska. In western and southwestern Nebraska, dissolution of volcanic glass is the most probable source of F Long residence times plus fluorite also may contribute to the F concentrations in the Chadron Formation.     

TOC Determinations in Ground Water

Determinations of total organic carbon (TOC) can provide valuable diagnostic evidence of the extent of ground-water contamination by organic compounds. The usefulness of conventional TOC results in monitoring efforts is limited by the bias introduced during the purging of inorganic carbon prior to analysis. A modified TOC procedure has been evaluated to permit the quantitation of the volatile organic carbon (VOC) fraction in water samples. The methodology consists of trapping the VOC in a manner analogous to commercial purge and trap instruments which are used for specific organic compound separations. The method has been found to be sensitive, accurate and reasonably precise for TOC determinations of standard solutions as well as on ground-water samples. Volatile organic carbon levels can range from 9–50% of the TOC in both uncontaminated and contaminated ground waters. The reporting of the volatile and nonvolatile fractions of the TOC will enhance both monitoring and research efforts, since it permits more complete characterization of the organic carbon content of ground-water samples.