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.     

Long-Term Confidence in Ground Water Monitoring Systems

State-of-the-art analytical techniques are capable of detecting contamination In the part per billion (ppb) range or lower. At these levels, a truly representative ground water sample Is essential to precisely evaluate ground water quality. The design specifications of a ground water monitoring system are critical in ensuring the collection of representative samples, particularly throughout the long-term monitoring period.
The potential interfaces from commonly used synthetic well casings require a thorough assessment of site, hydrogeology and the geochemical properties of ground water. Once designed, the monitoring system must be installed following guidelines that ensure adequate seals to prevent contaminant migration during the installation process or at some time in the future. Additionally, maintaining the system so the wells are in hydraulic connection with the monitored zone as well as periodically Inspecting the physical integrity of the system can prolong the usefulness of the wells for ground water quality. When ground water quality data become suspect due to potential interferences from existing monitoring wells, an appropriate abandonment technique must be employed to adequately remove or destroy the well while completely sealing the borehole.
The results of an inspection of a monitoring system comprised of six 4-inch diameter PVC monitoring wells at a hazardous well facility Indicated that the wells were improperly installed and in some cases provided a pathway for contamination. Subsequent down hole television inspections confirmed inaccuracies between construction logs and the existing system as well as identified defects in casing materials. An abandonment program was designed which destroyed the well casings in place while simultaneously providing a competent seal of the re-drilled borehole.     

Uplift and submarine formation of some Melanesian porphyry copper deposits: Stable isotope evidence

Hydrogen and oxygen isotope analyses of sericites and kaolinites from four young porphyry copper deposits (Ok Tedi (1.2 Ma) and Yandera (6.5 Ma), Papua New Guinea; Koloula (1.5 Ma), Solomon Islands; and Waisoi (<5 Ma), Fiji) indicate that the fluids from which these minerals precipitated were of mixed magmatic and non-magmatic sources. The non-magmatic component of the fluid from the island arc deposits (Koloula, Waisoi) was ocean water.For Ok Tedi, the non-magmatic component was a meteoric water with an isotopic composition different from that of the present meteoric water in the region. The isotopic signature of the former meteoric water is consistent with a surface elevation of 200 m a.s.l. or less at the time of mineralization. The deposit was later exposed and supergene kaolinitization commenced at approximately 1200 m a.s.l. Uplift and erosion has continued to the present at which time the elevation of the exposed deposit is 1800 m a.s.l. This rate of uplift is consistent with that known from other geological evidence. If the rate of uplift were approximately constant during the last 1.2 Ma, the age of supergene enrichment can be dated at approximately 0.4 Ma B.P.Similarly, influx of meteoric water at Yandera occurred when the ground surface above the deposit was at an elevation of approximately 600 m a.s.l. The deposit's present elevation is 1600 m a.s.l. In this case a total uplift of approximately 2.2 km is indicated, with removal of 1.2 km of overburden by erosion.     

Equilibrium bank geometry and the width of shallow sandbed streams

Cross-sections of 16 straight sandbed streams in Minnesota, Iowa, and Nebraska were surveyed. Two stratigraphic horizons were found in the banks at each site, an upper cohesive unit usually composed of silt and clay and a lower unit composed of sand. Bank erosion on these rivers occurs when the upper cohesive unit is undercut by scour at bends. The overhanging cohesive block fails by beam or cantilever failure. As upper bank failure is a direct result of undercutting, the stability and rate of retreat of the bank are largely determined by erosion of the sandy part of the bank. The cohesive layer has little influence on bank retreat and width adjustment on the rivers studied here. A quantitative lateral sediment transport model developed by Parker (1978a) is used to calculate the steady-state geometry of the sandy part of the bank. Results are obtained for the shape, length, and height of the sandy part of the bank. The model predicts the length of the bank fairly well, and the theoretical equation for the height of the bank is of the correct form. The model, however, overestimates the slope of the bank. The height of the sandy part of the bank (D_b) is approximately equal to the depth of the mean annual flow. Since D_b is determined by the lateral sediment transport model, the width (W) may be obtained from the equation of continuity (Q = WD_bV), published flow (Q) data, and a resistance equation for the mean velocity, V. The calculated widths are similar to those measured in the field.     

Specific-lon electrode determinations of sulfide preconcentrated from San Francisco Bay waters

Measurements of low-level dissolved-sulfide concentrations in estuarine water from San Francisco Bay have been made using the sulfide-specific electrode after preservation, separation, and preconcentration of the sulfide species. The separation and preconcentration were acheived by coprecipitation of ZnS with Zn(OH)₂ followed by collection and dissolution of the precipitate, giving concentration factors up to 160-fold Preconcentration provided sulfide solutions that were adequately measurable within the practical working range of the specific-ion electrode The sulfide detection limit with the preconcentration step is 0 02 μg/l Spike recoveries in the range of 81 to 10 1% have been achieved for laboratory-prepared samples having S²⁻ concentrations as low as 0 6 μg/l and 84 to 100% for an estuarine sample spiked in the field with 2 μg/l (S(−II) Positive correlations have been found between dissolved S(−II) concentrations and concentrations of dissolved Cd, Cu, and Ni, negative correlations have been found between bisulfide (HS⁻) activity and activities of Cd²⁺, Cu²⁺, and Ag⁺ species     

Boundary skin friction and sediment transport about an animal-tube mimic

ABSTRACT
A flume study was made of fluid flow, boundary skin friction, and sediment transport about an animal-tube mimic. The effect of a tube on momentum transfer depends most strongly on its height. A tube increases the net boundary skin friction locally and tends to promote sediment entrainment near its base. Flow in this region appears to be governed by the same similarity laws that apply to cylinders with much larger body Reynolds number. Particles travelling as suspended load may be deposited immediately downstream of the tube. The net sedimentological effect of any tube (i.e. deposition or scour) will depend both on its height and on the boundary shear stress imposed by the external flow. The near-wake region of a tube is dominated by a strong cross-stream exchange of momentum. Wake perturbations decay downstream seemingly in accordance with similarity laws which also govern mounted, two-dimensional structures.     

Thermodynamic stability studies of the basic copper carbonate mineral,malachite

Natural malachite is a well defined solid demonstrating reproducible solubility behavior over a wide range of pH. The following equilibrium constants associated with the malachite dissolution equilibrium at 25°C, 1 atm were determined:

(infinite dilution)

$\text{K}{}^1{}_{\mathrm{sp}}\text{=}\text{[Cu}{}^{\mathrm{2+}}\text{]}{}^2\text{[CO}{}^{\mathrm{2?}}{}_3\text{]K}{}^2{}_{\mathrm{w}}\text{a}{}^2{}_{\mathrm{H+}}\text{= 10. ± 0.2 × 10}{}^{\mathrm{?32}}$

(0.72 ionic strength)

(36.9‰ salinity seawater). The temperature dependence of a “mixed” equilibrium constant, K_sp⁺, of the form:

has been measured at I = 0.72, yielding the relationship:

$\text{log K}{}^2{}_{\mathrm{sp}}\text{= (? 9.8 ± 0.03) × 10}{}^4\text{(}\text{1}\text{T°K}\text{) + (1.52 ± 0.09)}$

within a 5–25°C temperature range. The effect of pressure on the solubility of malachite in water and seawater was estimated from partial molar volume and compressibility data. For 25 °C at infinite dilution $\text{K'}{}_{\mathrm{sp}}\text{(1000 bar)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 240}$ and in seawater $\text{K′}{}_{\mathrm{sp}}\text{(1000)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 44}$.Comparison of stoichiometric and apparent malachite equilibrium constants has been used to estimate the extent of copper(II) ion interaction at the ionic strength of seawater. In dilute carbonate medium (total alkalinity, TA = 2.4 meq/kg H₂O, pH 8.3), 2.9% of total dissolved copper exists as the free copper(II) ion and in seawater (S = 36.9%., TA = 2.3 meq/kg H₂O, pH = 8.1), $\text{[Cu}{}^{\mathrm{2+}}\text{]}\text{T(Cu)}$ is 3.1%.Total dissolved copper levels of approximately 450–750 nMol/Kg are necessary to attain malachite saturation conditions in the open ocean. Observations of malachite particles suspended in seawater must be explained by precipitation or solid phase substitution reactions from localized environments rather than by direct precipitation from bulk seawater.     

Context and environment in taphonomic analysis: Examples from Alaska's Porcupine River Caves

Field investigations of caves along Alaska's Porcupine River document three major mechanisms which modify bone in patterns similar to alterations produced by man: (1) carnivore fracture; (2) rodent gnawing; and (3) rock fall and rubble scarring. A late Wisconsin faunal assemblage composed of Equus sp., Rangifer tarandus, Ovis dalli, Bison sp., proboscidean, numerous small mammal species, birds, and fish is well documented. This faunal assemblage suggests a mosaic environment of grassland-tundra-forest in the immediate vicinity of these caves and implies that the late Wisconsin environment in north-central Alaska may have been characterized by a number of microenvironments and colder, dryer, steppe conditions. Taphonomic data which have historically been interpreted to support human occupation of eastern Beringia during the Pleistocene are critically examined and the context of these discoveries (not the specimens themselves) provides the test essential to document the antiquity of man in North America prior to 12,000 yr ago.     

Late Quaternary sapropel sediments in the eastern Mediterranean Sea: Faunal variations and chronology

Distinctive planktonic foraminiferal assemblages which characterize particular late Quaternary sapropel layers in deep basin sediments from the eastern Mediterranean Sea have been identified using cluster analysis. Three distinct clusters allow for identification and intercore correlation of the nine sapropels deposited during the last 250,000 yr. Cluster 1, representing sapropel layers S1 and S9, exhibits low abundances of Neogloboquadrina dutertrei and high abundances of Globigerinoides ruber; Cluster 2, which groups S3, S5, and S7, contains high abundances of G. ruber, N. dutertrei, and Globigerina bulloides, and Cluster 3, which includes samples from S4, S6, and S8, is marked by extremely abundant N. dutertrei and G. bulloides, and rare G. ruber. Analysis of sedimentation rates in 14 cores reveals the following approximate ages for the sapropel layers: S2 = 52,000 yr B.P.; S3 = 81,000–78,000 yr B.P.; S4 = 100,000–98,000 yr B.P.; and S5 = 125,000–116,000 yr B.P. As previously suggested, sedimentation rates on the Mediterranean Ridge were determined to be relatively constant during the last 127,000 yr. In contrast, basin sedimentation rates have fluctuated markedly from lower rates during interglacial stage 5 to higher rates during the last glacial episode. These glacial/interglacial differences are most pronounced in the northern Ionian Basin, because of increased terrigenous sediment deposition during glacial episodes. Unusually high biogenic sedimentation rates occurred in an arc south of Crete during the deposition of sapropel S5, probably due to higher productivity in this region.     

Characteristics of vertical turbulent velocities in the urban convective boundary layer

Turbulence measurements of the vertical velocity component were obtained by an instrumented aircraft under fair weather conditions in the St. Louis, Missouri, metropolitan area. Time series of vertical velocity fluctuations from horizontal flight segments made in the lower part of and near the middle of the convective boundary layer (CBL) over the urban area and surrounding region were subjected to various statistical and objective analyses. Higher order vertical velocity moments, and positive and negative velocity statistics, were computed. The horizontal dimensions of updrafts and downdrafts, and related properties of these turbulent eddies were derived by conditional sampling analysis. Emphasis is on a comparison of the results from urban and selected rural measurements from the lower part of the CBL.The vertical velocity probability density distribution for each segment was positively skewed and the mode was negative. The means and standard deviations of positive and negative velocity fluctuations were greater over the urban area. The urban vertical velocity variance was 50% greater than rural values, and power spectra revealed greater production of vertical turbulent energy in the urban area over a wide frequency range.The mean and maximum widths of downdrafts were generally larger than the corresponding values for updrafts. Differences between urban and rural eddy sizes were not statistically significant. The widths of the largest updraft and downdraft are comparable to the boundary-layer depth, Z _i, and the mean value of the ratio of spectral peak wavelength to Z _iwas about 1.3 and 1.1 for urban and rural areas, respectively. Convective similarity scaling parameters appeared to order both the urban and rural measurements.On assignment from the National Oceanic and Atmospheric Administration, U.S. Dept. of Commerce.