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Perchlorate (ClO4-) occurrence in groundwater has previously been linked to industrial releases and the historic use of Chilean nitrate fertilizers. However, recently a number of occurrences have been identified for which there is no obvious anthropogenic source. Groundwater from an area of 155 000 km2 in 56 counties in northwest Texas and eastern New Mexico is impacted by the presence of ClO4-. Concentrations were generally low (<4 ppb), although some areas are impacted by concentrations up to 200 ppb. ClO4- distribution is not related to well type (public water system, domestic, agricultural, or water-table monitoring) or aquifer (Ogallala, Edward Trinity High Plains, Edwards Trinity Plateau, Seymour, or Cenozoic). Results from vertically nested wells strongly indicate a surface source. The source of ClO4- appears to most likely be atmospheric deposition. Evidence supporting this hypothesis primarily relates to the presence of ClO 4- in tritium-free older water, the lack of relation between land use and concentration distribution, the inability of potential anthropogenic sources to account for the estimated mass of ClO4-, and the positive relationship between conserved anions (e.g., IO3-, Cl-, SO4-2) and ClO4-. The ClO4- distribution appears to be mainly related to evaporative concentration and unsaturated transport. This process has led to higher ClO4- and other ion concentrations in groundwater where the water table is relatively shallow, and in areas with lower saturated thickness. Irrigation may have accelerated this process in some areas by increasing the transport of accumulated salts and by increasing the number of evaporative cycles. Results from this study highlight the potential for ClO4- to impact groundwater in arid and semiarid areas through long-term atmospheric deposition. ?? 2006 American Chemical Society.
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The source of the background hydrocarbons in benthic sediments of Prince William Sound (PWS), AK, where the 1989 Exxon Valdez oil spill (EVOS) occurred, has been ascribed to oil seeps in coastal areas of the Gulf of Alaska (GOA). We present evidence that coal is a more plausible source, including (i) high concentrations of total PAH (TPAH), between 1670 and 3070 ng/g, in continental shelf sediments adjacent to the coastal region containing extensive coal deposits; (ii) PAH composition patterns of sediments along with predictive models that are consistent with coal but not oil; (iii) low ratios (<0.2) of triaromatic steranes to methylchrysenes found in sediments and coals, contrasting with the high ratios (11 and 13) found in seep oil; and (iv) bioaccumulation of PAH in salmon collected within 100 m of the Katalla oil seeps but not in filter-feeding mussels collected near oilfield drainages 9 km from the seeps, indicating negligible transport of bioavailable PAH from Katalla seeps to the GOA. In contrast with oil, PAH in coal are not bioavailable, so the presence of coal in these benthic sediments confers no adaptive benefit to biota of the marine ecosystem with respect to PAH insults from anthropogenic sources.The source of the background hydrocarbons in benthic sediments of Prince William Sound (PWS), AK, where the 1989 Exxon Valdez oil spill (EVOS) occurred, has been ascribed to oil seeps in coastal areas of the Gulf of Alaska (GOA). We present evidence that coal is a more plausible source, including (i) high concentrations of total PAH (TPAH), between 1670 and 3070 ng/g, in continental shelf sediments adjacent to the coastal region containing extensive coal deposits; (ii) PAH composition patterns of sediments along with predictive models that are consistent with coal but not oil; (iii) low ratios (<0.2) of triaromatic steranes to methylchrysenes found in sediments and coals, contrasting with the high ratios (11 and 13) found in seep oil; and (iv) bioaccumulation of PAH in salmon collected within 100 m of the Katalla oil seeps but not in filter-feeding mussels collected near oilfield drainages 9 km from the seeps, indicating negligible transport of bioavailable PAH from Katalla seeps to the GOA. In contrast with oil, PAH in coal are not bioavailable, so the presence of coal in these benthic sediments confers no adaptive benefit to biota of the marine ecosystem with respect to PAH insults from anthropogenic sources.
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The association constant for the dissolved species MnHCO 3 + was experimentally determined to be 63. From this value and a published constant for the species MNSO 4 aq., a diagram was prepared showing per cent of dissolved manganese complexed in the presence of 10 to 10,000 p.p.m. bicarbonate and 1.0 to 10,000 p.p.m. sulfate. The rate of oxidation of Mn +2 in aerated water is greatly increased by increasing pH, and is retarded when SO4 -2 and HCO 3 - are present.
Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufenacet [N-(4-fluorophenyl)-N-(1-methylethyl)-2-(5-(trifluoromethyl)-1,3,4- thiadiazol-2-yl)oxy] were isolated by C-18 solid-phase extraction and separated from their ethanesulfonic acid (ESA) and oxanilic acid (OXA) degradates during their elution using ethyl acetate for the parent compound, followed by methanol for the polar degradates. The parent compounds were detected using gas chromatography-mass spectrometry in selected-ion mode. The ESA and OXA degradates were detected using high-performance liquid chromatography-electrospray mass spectrometry (HPLC-ESPMS) in negative-ion mode. The method detection limits for a 123-mL sample ranged from 0.01 to 0.07 μg/L. These methods are compatible with existing methods and thus allow for analysis of 17 commonly used herbicides and 18 of their degradation compounds with one extraction. In a study of herbicide transport near the mouth of the Mississippi River during 1999 and 2000, dimethenamid and its ESA and OXA degradates were detected in surface water samples during the annual spring flushes. For flufenacet, the only detections at the study site were for the ESA degradates in samples collected at the peak of the herbicide spring flush in 2000. The low frequency of detections in surface water likely is due to dimethenamid and flufenacet being relatively new herbicides. In addition, detectable amounts of the stable degradates have not been detected in ground water.
Current conservation strategies for plant and animal species rarely address the need to protect the species throughout its geographic range thereby capturing potential genetic and ecological variation. We examined the degree that existing protected areas in the western United States satisfied this goal for four widespread vegetation cover types. We used latitude and longitude to stratify the distribution of these types into 16 cells, each of which was further stratified by up to five elevation classes. While protection of some vegetation types was high in parts of their range, it was minimal to nonexistent in other parts. While it is yet to be shown that protecting a given species throughout its geographic range is essential for its long-term existence, in the face of often unpredictable environmental changes, it seems a prudent course to follow. Our results suggest that if full range protection is a conservation goal, the existing network of protected areas may be inadequate for the task.
Measurements of the cosmogenically-produced 35 S, a radioisotope of sulphur (t 1/2 = 87 days), are reported for the Ned Wilson Lake watershed in Colorado. The watershed contains two small lakes and a flowing spring presumed to be representative of local ground water. The watershed is located in the Flattops Wilderness Area and the waters in the system have low alkalinity, making them sensitive to increases in acid and sulphate deposition. Time series of 35 S measurements were made during the summers of 1995 and 1996 (July–September) at all three sites. The system is dominated by melting snow and an initial concentration of 16–20 mBq L -1 was estimated for snowmelt based on a series of snow samples collected in the Rocky Mountains. The two lakes had large initial 35 S concentrations in July, indicating that a large fraction of the lake water and sulphate was introduced by meltwater from that year's snowpack. In 1995 and 1996, 35 S concentrations decreased more rapidly than could be accounted for by decay, indicating that other processes were affecting 35 S concentrations. The most likely explanation is that exchange with sediments or the biota was removing 35 S from the lake and replacing it with older sulphate devoid of 35 S. In September of 1995 and 1996, 35 S concentrations increased, suggesting that atmospheric deposition is important in the sulphate flux of these lakes in late summer. Sulphur-35 concentrations in the spring water were highly variable but never higher than 3.6 mBq L -1 and averaged 2 mBq L -1 . Using a simple mixing model, it was estimated that 75% of the spring water was derived from precipitation of previous years.
In the 20 years since cleanup of contaminated groundwater has been a high priority in the United States, recognition of both the scope of the problem and the technical difficulties involved has grown steadily. Estimates of the number of hazardous waste sites where groundwater may be contaminated vary between 300,000 and 400,000 nationwide [NRC, 1994]. Legislation passed in the 1980s by Congress and the states generally required that groundwater in contaminated aquifers be restored to background or drinking water standards. Unfortunately, attempts to meet these goals using conventional methods, such as pump and treat systems, frequently have been unsuccessful [NRC, 1994].
The main borehole of the German Continental Deep Drilling Program (KTB) extends over 9000 m into a crystalline upper crust consisting primarily of interlayered gneiss and metabasite. We present a joint analysis of the velocity and lithology logs in an effort to extract the lithology component of the velocity log. Covariance analysis of lithology log, approximated as a binary series, indicates that it may originate from the superposition of two Brownian stochastic processes (fractal dimension 1.5) with characteristic scales of ∼2800 m and ∼150 m, respectively. Covariance analysis of the velocity fluctuations provides evidence for the superposition of four stochastic process with distinct characteristic scales. The largest two scales are identical to those derived from the lithology, confirming that these scales of velocity heterogeneity are caused by lithology variations. The third characteristic scale, ∼20 m, also a Brownian process, is probably related to fracturing based on correlation with the resistivity log. The superposition of these three Brownian processes closely mimics the commonly observed 1/ k decay (fractal dimension 2.0) of the velocity power spectrum. The smallest scale process (characteristic scale ∼1.7 m) requires a low fractal dimension, ∼1.0, and accounts for ∼60% of the total rms velocity variation. A comparison of successive logs from 6900–7140 m depth indicates that such variations are not repeatable and thus probably do not represent true velocity variations in the crust. The results of this study resolve disparity between the differing published estimates of seismic heterogeneity based on the KTB sonic logs, and bridge the gap between estimates of crustal heterogeneity from geologic maps and borehole logs.
The stability of submarine gas hydrates is largely dictated by pressure and temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of deep marine sediments may also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our conceptual model presumes that gas hydrate behaves in a way analogous to ice in a freezing soil. Hydrate growth is inhibited within fine-grained sediments by a combination of reduced pore water activity in the vicinity of hydrophilic mineral surfaces, and the excess internal energy of small crystals confined in pores. The excess energy can be thought of as a "capillary pressure" in the hydrate crystal, related to the pore size distribution and the state of stress in the sediment framework. The base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature (nearer to the seabed) than would be calculated from bulk thermodynamic equilibrium. Capillary effects or a build up of salt in the system can expand the phase boundary between hydrate and free gas into a divariant field extending over a finite depth range dictated by total methane content and pore-size distribution. Hysteresis between the temperatures of crystallization and dissociation of the clathrate is also predicted. Growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, and lenses in muds; cements in sands) can largely be explained by capillary effects, but kinetics of nucleation and growth are also important. The formation of concentrated gas hydrates in a partially closed system with respect to material transport, or where gas can flush through the system, may lead to water depletion in the host sediment. This "freeze-drying" may be detectable through physical changes to the sediment (low water content and overconsolidation) and/or chemical anomalies in the pore waters and metastable presence of free gas within the normal zone of hydrate stability.