The role of humic non-exchangeable binding in the promotion of metal ion transport in groundwaters in the environment

Metal ions form strong complexes with humic substances. When the metal ion is first complexed by humic material, it is bound in an 'exchangeable' mode. The metal ion in this fraction is strongly bound, however, if the metal-humic complex encounters a stronger binding site on a surface, then the metal ion may dissociate from the humic substance and be immobilised. However, over time, exchangeably-bound metal may transfer to a 'non-exchangeable' mode. Transfer into this mode and dissociation from it are slow, regardless of the strength of the competing sink, and so immobilisation may be hindered. A series of coupled chemical transport calculations has been performed to investigate the likely effects of non-exchangeable binding upon the transport of metal ions in the environment. The calculations show that metal in the non-exchangeable mode will have a significantly higher mobility than that in the exchangeable mode. The critical factor is the ratio of the non-exchangeable first-order dissociation rate constant and the residence time in the groundwater column, metal ion mobility increasing with decreasing rate constant. A second series of calculations has investigated the effect of the sorption to surfaces of humic/metal complexes on the transport of the non-exchangeably bound metal. It was found that such sorption may reduce mobility, depending upon the humic fraction to which the metal ion is bound. For the more weakly sorbing humic fractions, under ambient conditions (humic concentration etc.) the non-exchangeable fraction may still transport significantly. However, for the more strongly sorbed fractions, the non-exchangeable fraction has little effect upon mobility. In addition to direct retardation, sorption also increases the residence time of the non-exchangeable fraction, giving more time for dissociation and immobilisation. The non-exchangeable dissociation reaction, and the sorption reaction have been classified in terms of two Damkohler numbers, which can be used to determine the importance of chemical kinetics during transport calculations. These numbers have been used to develop a set of rules that determine when full chemical kinetic calculations are required for a reliable prediction, and when equilibrium may be assumed, or when the reactions are sufficiently slow that they may be ignored completely.     

A Comparison Study of Various Types of Ozone and Oxidant Detectors Which Are Used for Atmospheric Air Sampling

Four continuous automatic analyzers for measurement of atmospheric levels of ozone were used in a calibration and field study. These were (1) a colorimetric instrument based upon detection of iodine released from neutral potassium iodide reagent, {2) a coulometric instrument utilizing the polarization current as a measurement of iodine released by ozone in a cell contacted by potassium iodide reagent, (8) a galvanic cell measuring bromine release by ozone, and (4) an ultraviolet photometer. Some ozone determinations by the manual rubber cracking procedure were included. After calibration with ozone the average relative response to atmospheric ozone levels for each instrument was determined using the colorimetric oxidant analyzer as an arbitrary standard. These responses ranged from 77 percent for the galvanic cell 90 percent for the photometer. The instrument of choice for any given application would seem to be governed by requirements for precision specificity, portability, reliability, and ease of operation.     

The Recovery of Ammonia and Hydrogen Sulflde from Ground-Level Area Sources Using Dynamic Isolation Flux Chambers: Bench-Scale Studies

Abstract

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH₃) and hydrogen sulflde (H₂S) from dynamic isolation flux chambers. H₂S (80–4000 ppb) and NH₃ (5000–40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H₂S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H₂S could be recovered during the given sampling period. NH₃ emissions exhibited similar behavior between concentrations of 5000–40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH₃ sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH₃ or H₂S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH₃ and H₂S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH₃ and H₂S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the full-scale sensitivity of the gas sensing equipment. The use of 46–90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Influence of mercury and selenium chemistries on the progression of cardiomyopathy in pygmy sperm whales, Kogia breviceps

More than half of pygmy sperm whales (Kogia breviceps) that strand exhibit signs of cardiomyopathy (CMP). Many factors may contribute to the development of idiopathic CMP in K. breviceps, including genetics, infectious agents, contaminants, biotoxins, and dietary intake (e.g. selenium, mercury, and pro-oxidants). This study assessed trace elements in K. breviceps at various stages of CMP progression using fresh frozen liver and heart samples collected from individuals that stranded along US Atlantic and Gulf coasts between 1993 and 2007. Standard addition calibration and collision cell inductively coupled plasma mass spectrometry (ICP-MS) were employed for total Se analysis and pyrolysis atomic absorption (AA) was utilized for total Hg analysis to examine if the Se/Hg detoxification pathway inhibits the bioavailability of Se. Double spike speciated isotope dilution gas chromatography ICP-MS was utilized to measure methyl Hg and inorganic Hg. Immunoblot detection and colorimetric assays were used to assess protein oxidation status. Data collected on trace elements, selenoproteins, and oxidative status were evaluated in the context of animal life history and other complementary histological information to gain insight into the biochemical pathways contributing to the development of CMP in K. breviceps. Cardiomyopathy was only observed in adult pygmy sperm whales, predominantly in male animals. Both Hg:Se molar ratios and overall protein oxidation were greater in males than females and increased with progression of CMP.     

Links among nitrification, nitrifier communities, and edaphic properties in contrasting soils receiving dairy slurry

Soil biotic and abiotic factors strongly influence nitrogen (N) availability and increases in nitrification rates associated with the application of manure. In this study, we examine the effects of edaphic properties and a dairy (Bos taurus) slurry amendment on N availability, nitrification rates and nitrifier communities. Soils of variable texture and clay mineralogy were collected from six USDA-ARS research sites and incubated for 28 d with and without dairy slurry applied at a rate of ~300 kg N ha(-1). Periodically, subsamples were removed for analyses of 2 M KCl extractable N and nitrification potential, as well as gene copy numbers of ammonia-oxidizing bacteria (AOB) and archaea (AOA). Spearman coefficients for nitrification potentials and AOB copy number were positively correlated with total soil C, total soil N, cation exchange capacity, and clay mineralogy in treatments with and without slurry application. Our data show that the quantity and type of clay minerals present in a soil affect nitrifier populations, nitrification rates, and the release of inorganic N. Nitrogen mineralization, nitrification potentials, and edaphic properties were positively correlated with AOB gene copy numbers. On average, AOA gene copy numbers were an order of magnitude lower than those of AOB across the six soils and did not increase with slurry application. Our research suggests that the two nitrifier communities overlap but have different optimum environmental conditions for growth and activity that are partly determined by the interaction of manure-derived ammonium with soil properties.     

Sediment amendment with Phoslock® in Clatto Reservoir (Dundee, UK): Investigating changes in sediment elemental composition and phosphorus fractionation

Lanthanum-modified bentonite clay (Phoslock(?) is a lake remediation tool designed to strip dissolved phosphorus (P) from the water column and increase the sediment P-sorption capacity. This study investigated short term alterations in sediment elemental composition and sediment P-fractions based on sediment cores taken 2 days before and 28 days following the application of 24 t of Phoslock? to a 9 ha, man-made reservoir. Following the application, sediment lanthanum (La) content increased significantly (p < 0.05; n = 4) in the top 8 cm of the sediment, thereby theoretically increasing sediment P-binding capacity on the whole reservoir scale by 250 kg. Mass balance calculations were used to estimate the theoretical binding of release-sensitive P (P(mobile); sum of 'labile P', 'reductant-soluble P' and 'organic P' fraction) by La across the top 4 cm and 10 cm depth of sediment. The amended mass of La in the sediment had the potential to bind 42% of P(mobile) present in the top 4 cm or 17% of P(mobile) present in the top 10 cm. However, with the exception of a significant increase (p<0.05; n=4) in the 'residual P' fraction in the top 2 cm, sediment P-fractions, including P(mobile,) did not differ significantly following the Phoslock? application. Experimental P-adsorption studies indicated P-saturation values for Phoslock? of 21,670 mg P kg?1 Phoslock?. Sequential extraction of P from saturated Phoslock? under laboratory conditions indicated that around 21% of P bound by Phoslock? was release-sensitive, while around 79% of bound P was unlikely to be released under reducing or common pH (5-9) conditions in shallow lakes. Applying Phoslock? is, therefore, likely to increase the P-sorption capacity of sediments under reducing conditions.     

Do Postfire Mulching Treatments Affect Plant Community Recovery in California Coastal Sage Scrub Lands?

In recent years, the use of postfire mulch treatments to stabilize slopes and reduce soil erosion in shrubland ecosystems has increased; however, the potential effects on plant recovery have not been examined. To evaluate the effects of mulching treatments on postfire plant recovery in southern California coastal sage scrub, we conducted a field experiment with three experimental treatments, consisting of two hydromulch products and an erosion control blanket, plus a control treatment. The area burned in 2007, and treatments were applied to six plot blocks before the 2008 growing season. Treatment effects on plant community recovery were analyzed with a mixed effects ANOVA analysis using a univariate repeated measures approach. Absolute plant cover increased from 13 to 90% by the end of the second growing season, and the mean relative cover of exotic species was 32%. The two hydromulch treatments had no effect on any plant community recovery response variable measured. For the erosion control blanket treatment, the amount of bare ground cover at the end of the second growing season was significantly lower (P = 0.01), and greater shrub height was observed (P < 0.01). We conclude that postfire mulch treatments did not provide either a major benefit or negative impact to coastal sage scrub recovery on the study area.     

The impact of the 2005 Gulf hurricanes on pollution emissions as inferred from Ozone Monitoring Instrument (OMI) nitrogen dioxide

The impact of Hurricanes Katrina and Rita in 2005 on pollution emissions in the Gulf of Mexico region was investigated using tropospheric column amounts of nitrogen dioxide (NO₂) from the Ozone Monitoring Instrument (OMI) on the NASA Aura satellite. Around New Orleans and coastal Mississippi, we estimate that Katrina caused a 35% reduction in NO_x emissions on average in the three weeks after landfall. Hurricane Rita caused a significant reduction (20%) in NO_x emissions associated with power generation and intensive oil refining activities near the Texas/Louisiana border. We also found a 43% decrease by these two storms over the eastern Gulf of Mexico Outer Continental Shelf mainly due to the evacuation of and damage to platforms, rigs, and ports associated with oil and natural gas production.     

Use of toxicity identification evaluations to determine the pesticide mitigation effectiveness of on-farm vegetated treatment systems

Evidence of ecological impacts from pesticide runoff has prompted installation of vegetated treatment systems (VTS) along the central coast of California, USA. During five surveys of two on-farm VTS ponds, 88% of inlet and outlet water samples were toxic to Ceriodaphnia dubia. Toxicity identification evaluations (TIEs) indicated water toxicity was caused by diazinon at VTS-1, and chlorpyrifos at VTS-2. Diazinon levels in VTS-1 were variable, but high pulse inflow concentrations were reduced through dilution. At VTS-2, chlorpyrifos concentrations averaged 52% lower at the VTS outlet than at the inlet. Water concentrations of most other pesticides averaged 20-90% lower at VTS outlets. All VTS sediment samples were toxic to amphipods (Hyalella azteca). Sediment TIEs indicated toxicity was caused by cypermethrin and lambda-cyhalothrin at VTS-1, and chlorpyrifos and permethrin at VTS-2. As with water, sediment concentrations were lower at VTS outlets, indicating substantial reductions in farm runoff pesticide concentrations.     

Quantifying Diffuse Pollution Sources and Loads for Environmental Quality Standards in Urban Catchments

The paper explores the application of a unit area loading (UAL) approach to address the requirements of the US Clean Water Act (CWA) and the EU Water Framework Directive (WFD) for the identification and quantification of diffuse urban pollution sources. The UAL approach defines the spatial distribution of pollutant loadings within an urban catchment as a basis for the assessment of in-stream hazards and the implementation of source control BMP measures. Calculated annual outflow concentrations for a specific catchment for two pollutants, zinc and hydrocarbons, illustrate the different levels of dilution/control, which can be required to achieve receiving water quality standards and objectives. Methodological issues relating to traditional volume-concentration probabilistic modelling on which the UAL approach is based are discussed, and the application of the UAL approach to non-point diffuse pollution load management is reviewed.