The contribution of humic substances to the acidity of colored natural waters

An operationally defined carboxyl content of humic substances extracted from rivers, streams, lakes, wetlands, and groundwaters throughout the United States and Canada is reported. Despite the diversity of the samples, only small variations were observed in this humic carboxyl content. The dissociation behavior of two combined fulvic/humic acid extracts was studied and it was found that the dissociation of the humics varied in a predictable manner with pH. Using a carboxyl content of 10 μeq/ mg humic organic carbon, and mass action quotient calculated from sample pH, the ionic balances of three highly colored Nova Scotia rivers were estimated.     

Terbuthylazine and Deethylterbuthylazine in Rain and Surface Water – Determination by Enzyme Immunoassay and Gas Chromatography/Mass Spectrometry

Rain and surface water samples from Southern Germany were investigated from 1991 to 1995 for terbuthylazine and one of its major metabolites, deethylterbuthylazine. The concentrations observed were compared to the concentrations found for atrazine and deethylatrazine in the same water samples. Concentrations ranged from < 0.02 μg/L to 0.7 μg/L for terbuthylazine and from < 0.02 μg/L to 0.6 μg/L for deethylterbuthylazine, compared to concentrations of < 0.02 μg/L to 3 μg/L and < 0.02 μg/L to 0.5 μg/L for atrazine and deethylatrazine, respectively. The ratios of metabolite concentrations to parent compound concentrations were calculated for deethylterbuthylazine to terbuthylazine (DTR) and deethylatrazine to atrazine (DAR). In rain water, DTR of 0.8…3.0 and DAR of 0.3… 1.9 were determined with mean values of 0.9… 1.7 for DTR and 0.6…0.9 for DAR in the different years. The ratios increased during summer periods. The highest ratios were observed in samples from forest stands, showing that degradation of the herbicide has occurred during transport between the source and the sampling site. The DTR in rain water were about 50… 100% higher than the DAR. This indicates a higher degradation rate of terbuthylazine during atmospheric transport. In surface water, DTR of 0.3… 1.2 with mean values of 0.5…0.8 and DAR of 0.2…2.2 with mean values of 0.2… 1.3 were observed. The ratios increased from June to September.     

Non-linear elastic behaviour of damaged rocks

The pervasive damage of rocks by microcracks and voids strongly affects their macroscopic elastic properties. To evaluate the damage effects, we derive here the macroscopic stress-strain relations for a 3-D elastic solid with non-interacting cracks embedded inside a homogeneous matrix. The cracks considered are oriented either perpendicular to the maximum tension axis, or perpendicular to the maximum compression axis. In the first case they dilate during loading and in the second case they contract during loading. We derive a solution for the elastic energy of this rock following the self-consistent scheme of Budiansky & O'Connell (1976). The solution describes the stress-strain relations in terms of Λ^d and μ^d, which are the modified Lame constants, and an additional parameter Λ. The latter accounts for the non-linear behaviour of the solid and is related to crack density. The solution predicts a non-linear elastic rheology even for an infinitesimal strain of ɛ < 0.001, and abrupt change in the elastic moduli when the loading reverses from uniaxial compression to uniaxial tension.
We use the derived solution to analyse rock-mechanics experiments in which beams of Indiana limestone were deformed under four-point loading. This configuration provides simultaneously the apparent tensile and compressive moduli for small strains. The apparent moduli fit the effective elastic moduli calculated with the present damage model well, including the differences between tensile and compressive moduli.     

Osmoregulation in Six Sympatric Fiddler Crabs (genus Uca) from the Northwestern Gulf of Mexico

Abstract. As problems in taxonomy and systematic relationships among the Uca species are resolved, a definition of how each fiddler crab species partitions and utilizes habitat resources is needed. To this end, the osmoregulatory capabilities were studied in six species of fiddler crabs from the western Gulf of Mexico. Specimens were placed in 50  ml of artificial seawater ranging in osmolality from 50 to 3450  mOsm (2 to 109  ‰) for five days. Survivorship was recorded for each species. Uca rapax, U. panacea and U. subcylindrica are hardy from 200 to 3200  mOsm (6 to 101  ‰). Uca spinicarpa and U. minax survive only below 1400  mOsm (44  ‰). U. longisignalis is intermediate, with limited survival above 2500  mOsm (79  ‰). Hemolymph osmolality was determined for crabs surviving the osmotic regimen. Uca panacea, U. subcylindrica and U. rapax are equivalent in their regulation between 50 and 3200  mOsm (2 – 101  ‰). Uca longisignalis lost its ability to control hemolymph osmolality above 2200  mOsm (69  ‰). On the other hand , U. spinicarpa and U. minax become less effective hyporegulators in media above 1200 (38  ‰) and 1500  mOsm (47  ‰), respectively. Only U. longisignalis appears to exhibit clear differences in osmoregulatory capacity between populations. Population data for U. panacea and laboratory experiments with U. subcylindrica also support the notion of capacitative acclimation in Uca . These physiological capabilities correlate well with the known habitat characteristics for each fiddler crab species in the northwestern Gulf of Mexico.     

Methods for evaluating in-stream attenuation of trace organic compounds

Wastewater treatment plants are often the most substantial contributor of trace organic compounds including pharmaceuticals, steroidal hormones, and surfactants to surface waters. Studying stream reaches below wastewater treatment plants provide valuable information on the environmental persistence of these compounds. Three methods for conducting field investigations to evaluate in-stream attenuation of trace organic compounds are presented: (1) using intrinsic tracers in wastewater, (2) environmental sampling coupled with dye studies to assess travel times between sample locations, and (3) Lagrangian sampling. Advantages and limitations of each method are discussed, along with key findings from several investigations.     

Molecular size of aquatic humic substances

Aquatic humic substances, which account for 30 to 50% of the organic carbon in water, are a principal component of aquatic organic matter. The molecular size of aquatic humic substances, determined by small-angle X-ray scattering, varies from 4.7 to 33 Å in their radius of gyration, corresponding to a molecular weight range of 500 to greater than 10,000. The aquatic fulvic acid fraction contains substances with molecular weights ranging from 500 to 2000 and is monodisperse, whereas the aquatic humic acid fraction contains substances with molecular weights ranging from 1000 to greater than 10,000 and is generally polydisperse.     

Faecal indicators and pathogens in selected New Zealand waterfowl

Freshly excreted droppings from Canada geese (n=80), black swans (n=80), ducks (n=80) and gulls (n=80) were collected from sites around New Zealand. The droppings were enumerated for Escherichia coli, enterococci and Salmonella spp., and for the presence/absence of Cryptosporidium spp. Overall prevalence of E. coli and enterococci in samples was 95% and 94%, respectively. Cryptosporidium spp. was detected in 2% of the samples, whereas no Salmonella spp. were detected in the survey. Preliminary estimates of daily microbial outputs suggest that ducks will produce the highest loadings of E. coli and enterococci per bird, whereas Canada geese will produce the highest loadings of Campylobacter spp. per bird. This study provides the first set of indicator and pathogen counts for one of the largest sources of diffuse faecal contamination of natural waters in New Zealand.     

Degradates provide insight to spatial and temporal trends of herbicides in ground water

Since 1995, a network of municipal wells in Iowa, representing all major aquifer types (alluvial, bedrock/karst region, glacial drift, bedrock/nonkarst region), has been repeatedly sampled for a broad suite of herbicide compounds yielding one of the most comprehensive statewide databases of such compounds currently available in the United States. This dataset is ideal for documenting the insight that herbicide degradates provide to the spatial and temporal distribution of herbicides in ground water. During 2001, 86 municipal wells in Iowa were sampled and analyzed for 21 herbicide parent compounds and 24 herbicide degradates. The frequency of detection increased from 17% when only herbicide parent compounds were considered to 53% when both herbicide parents and degradates were considered. Thus, the transport of herbicide compounds to ground water is substantially underestimated when herbicide degradates are not considered. A significant difference in the results among the major aquifer types was apparent only when both herbicide parent compounds and their degradates were considered. In addition, including herbicide degradates greatly improved the statistical relation to the age of the water being sampled. When herbicide parent compounds are considered, only 40% of the wells lacking a herbicide detection could be explained by the age of the water predating herbicide use. However, when herbicide degradates were also considered, 80% of the ground water samples lacking a detection could be explained by the age of the water predating herbicide use. Finally, a temporal pattern in alachlor concentrations in ground water could only be identified when alachlor degradates were considered.     

Acid neutralizing processes in an alpine watershed front range, Colorado, U.S.A.—1: Buffering capacity of dissolved organic carbon in soil solutions

Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai⁻, derived from DOC at sample pH and the concentration of organic anion, Ax⁻ at the equivalence point were calculated using car☐yl contents from isolated and purified humic material from soil solutions. Subtracting Ax⁻ from Ai⁻ yields the contribution of humic substances to the buffering capacity (A_equiv.⁻). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado.     

Pyrolysis-mass spectrometry/pattern recognition on a well-characterized suite of humic samples

A suite of well-characterized humic and fulvic acids of freshwater, soil and plant origin was subjected to pyrolysis-mass spectrometry and the resulting data were analyzed by pattern recognition and factor analysis. A factor analysis plot of the data shows that the humic acids and fulvic acids can be segregated into two distinct classes. Carbohydrate and phenolic components are more pronounced in the pyrolysis products of the fulvic acids, and saturated and unsaturated hydrocarbons contribute more to the humic acid pyrolysis products. A second factor analysis plot shows a separation which appears to be based primarily on whether the samples are of aquatic or soil origin.