Reproducibility of the BCR sequential extraction procedure in a long-term study of the association of heavy metals with soil components in an upland catchment in Scotland

Humic iron podzol soils from three different plots at the Glensaugh Research Station, Aberdeenshire have been sampled on an annual basis since 1990 and analysed using both total digestion and the original BCR sequential extraction procedure. Particular care was required during the oxidation of these organic soils to prevent loss of material. The residue from the sequential extraction was analysed so that the values for total concentration derived from the total digestion and from the sum of the concentrations in the fractions of the extraction procedure could be compared. The comparison was good for all three soils indicating that not only did the sequential extraction give good recovery but that this was reproducible over a period of several years. The proportion of metals extractable at each step remained relatively constant thereby demonstrating the reproducibility of the procedure and the stability of the metals in the soils over the time scale of the sampling used. Whereas the total concentrations of Cr, Cu and Ni were highest in the soil from a roadside plot, this was not the case for Cd, Pb and Zn. In the case of Pb, concentrations in soils (0-25-cm depth) well away from the road were over 100 mg/kg and well above the expected background level. The distribution of metals between each of the extracted fractions varied not only between each metal but also between each of the three soils indicating that both metal and soil influenced the measured distribution. The distribution of Pb in the roadside soil was different from those in the other two soils and over 10% was extracted in the first, acetic acid soluble, fraction.     

Coagulation dynamics of fractal flocs induced by enmeshment and electrostatic patch mechanisms

The size and structure of flocs during floc formation were monitored for various coagulation mechanisms. Two distinctive mechanisms, namely, enmeshment and electrostatic patch, govern the dynamics of kaolin particles coagulation by polyaluminum chloride (PACl). They were investigated by small angle static light scattering (SASLS) and solid-state ²⁷Al NMR. In addition, a novel wet SEM (WSEM) was used in-situ to image the morphology of the aggregate in aqueous solution. Synthetic suspended particles were coagulated by two PACl products, a commercial product (PACl) and one laboratory product (PACl-E). The PACl-E contained more than 60% Al₁₃ while the PACl contained only 7% Al₁₃, with large percentage of colloidal Al. For coagulation by PACl at neutral pH and high dosage where the strong repulsion between particles occurs, the enmeshment ruled by reaction-limited aggregation (RLA) results in larger sweep flocs as well as higher fractal dimensional structure. For coagulation by PACl-E at alkaline pH and low dosage, the flocs were coagulated predominately by electrostatic patch with Al₁₃ aggregates. At such condition, it is likely that diffusion-limited aggregation (DLA) predominately rule PACl-E coagulation. The fractal dimension (D_s) values of PACl and PACl-E flocs formed at enmeshment and electrostatic patch increased with dosage, respectively. When breakage of flocs occurs, the breakage rate of PACl-E flocs is slower than that of sweep flocs. By WSEM imaging, the adsorption of spherical Al precipitates onto the particles was observed to form sweep flocs with a rough and ragged contour, while the PACl-E flocs were formed with a smooth and glossy structure.     

DBP formation kinetics in a simulated distribution system

Little is known about how the growth of halogenated disinfection by-products (DBPs) in drinking water is affected by time spent in a distribution system. Experiments were performed to compare the rate of trihalomethane and haloacetic acid production in a simulated pipe environment to that observed for the same water held in glass bottles. Results showed that although the rate of chlorine consumption in the pipe was much greater than in the bottle, there was no decrease in the amount of haloacetic acids produced and that trihalomethane levels actually increased by an average of 15%. Separate tests confirmed that this increase was due to a reservoir of organic precursor material associated with deposits on the pipe wall. This work suggests that the rate of DBP production in a distribution system will not necessarily be reduced by increased chlorine consumption due to non-DBP producing reactions with deposits on the pipe wall.     

A model of homeless migration: homeless men in Skid Row,Los Angeles

"In this paper a conceptual model of homeless migration is developed that links migration behavior with the coping status of homeless individuals. The model is evaluated by using data drawn from a recent random probability sample of men surveyed in Skid Row, Los Angeles, [California]. Results indicate that homeless migrants tended to be young, never married, white, mentally disabled, and either newly or cyclically homeless individuals. Long-term residents, in contrast, were apt to be older, physically disabled or suffering from a health-related problem, and had been homeless for some time. The dominant reason given for moving was to find a job...." Coping strategies and migration behaviors are also described.     

Design of an aquatic biomonitoring network for an environmental specimen bank

The aim of the present study was to establish an aquatic biomonitoring network for the Galician Environmental Specimen Bank (BEAG) (NW Spain). For this, a sampling system was designed that comprised of 121 points distributed throughout Galician rivers, from which samples of water and of three species of bryophytes were collected. The results obtained allowed selection of 74 sampling points and 2 species (Fontinalis antipyretica Hedw. and F. squamosa Hedw.) as the most suitable for use in future BEAG sampling surveys. The two species selected showed a strong similarity in their capacity to accumulate the 17 elements determined (Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Pb, Se and Zn), as well as in their ecological preferences. Furthermore, the levels of contamination of epicontinental waters were lower than those observed in previous surveys.     

Mechanisms for naphthalene removal during electrolytic aeration

Batch tests were performed to investigate chemical and physical processes that may result during electrolytic aeration of a contaminated aquifer using naphthalene as a model contaminant. Naphthalene degradation of 58-66% took place electrolytically and occurred at the same rates at a pH of 4 and 7. 1,4-naphthoquinone was identified as a product of the electrolysis. Stripping due to gases produced at the electrodes did not result in any naphthalene loss. Hydrogen peroxide (which may be produced at the cathode) did not have any effect on naphthalene, but the addition of ferrous iron (which may be present in aquifers) resulted in 67-99% disappearance of naphthalene. Chlorine (which may be produced from the anodic oxidation of chloride) can effectively degrade naphthalene at pH of 4, but not at a pH of 7. Mono-, di- and poly chloronaphthalenes were identified as oxidation products. Ferric iron coagulation (due to the oxidation of ferrous iron) did not significantly contribute to naphthalene loss. Overall, electrolytic oxidation and chemical oxidation due to the electrolytic by-products formed are significant abiotic processes that could occur and should be accounted for if bioremediation of PAH-contaminated sites via electrolytic aeration is considered. Possible undesirable products such as chlorinated compounds may be formed when significant amounts of chlorides are present.     

Mercury methylation and bacterial activity associated to tropical phytoplankton

The methylated form of mercury (Hg), methylmercury (MeHg), is one of the most toxic pollutants. Biotic and/or abiotic methylation, often associated to sulfate-reducing bacteria metabolism, occurs in aquatic environments and in many tropical areas, mostly in the periphyton associated to floating macrophyte roots. Data about mercury methylation by phytoplankton are scarce and the aim of this study was to verify the biotic influence in the methylation process in Microcystis aeruginosa and Sineccocystis sp. laboratory strains and in natural populations of phytoplankton from two different aquatic systems, the mesotrophic Ribeir?o das Lajes reservoir and hypereutrophic oligohaline Jacarepaguá lagoon, Rio de Janeiro state, Brazil. Adapted radiochemical techniques were used to measure sulfate-reduction, mercury methylation and bacterial activity in phytoplankton samples. Methyl-(203)Hg formation from added inorganic (203)Hg and (3)H-Leucine uptake were measured by liquid scintillation as well as sulfate-reduction, estimated as H(2)(35)S produced from added Na(2)(35)SO(4). There was no significant difference in low methylation potentials (0.37%) among the two cyanobacterium species studied in laboratory conditions. At Ribeir?o das Lajes reservoir, there was no significant difference in methylation, bacterial activity and sulfate-reduction of surface sediment between the sampling points. Methylation in sediments (3-4%) was higher than in phytoplankton (1.5%), the opposite being true for bacterial activity (sediment mean 6.6 against 150.3 nmol gdw(-1) h(-1) for phytoplankton samples). At Jacarepaguá lagoon, an expressive bacterial activity (477.1 x 10(3) nmol gdw(-1) h(-1) at a concentration of 1000 nM leucine) and sulfate-reduction ( approximately 21% H(2)(35)S trapped) associated to phytoplankton (mostly cyanobacteria M. aeruginosa) was observed, but mercury methylation was not detected.     

Effects of time and point-of-use devices on arsenic levels in Southeastern Michigan drinking water, USA

Health effects associated with chronic, low-level exposures to arsenic in drinking water (<100 microg/L) remain unclear, in part due to uncertainties in assessing exposure. Drinking water concentrations have been used to assess past exposure to arsenic in epidemiological studies, under the assumption that a single measurement can be used to estimate historical exposure. This study aims to better understand (1) temporal variability in arsenic concentrations in drinking water and (2) the impact of point-of-use (POU) treatment devices on arsenic exposure measurements, and on reliability of the exposure measurement for population-level studies. Multiple drinking water samples were collected at two points in time (an average of fourteen months apart) for 261 individuals enrolled in a case-control study of arsenic exposure and bladder cancer in Michigan. Sources of drinking water included private wells (n = 221), public water supplies (n = 33), and bottled water (n = 7); mean arsenic concentration was highest in private wells (7.28 microg/L) and lowest in bottled water samples (0.28 microg/L). Arsenic concentrations in primary drinking water samples were highly correlated (r = 0.88, p < 0.0001, n = 196), with 3% of the water sources exceeding the United States Environmental Protection Agency's Maximum Contaminant Level (MCL) in one sample but not in the other sample. Measurement reproducibility did not vary by type of POU device (e.g., softener, filter, reverse osmosis system). Arsenic concentrations did differ, however, between samples treated with POU devices and untreated samples taken on the same day. Substantial differences in arsenic concentrations were consistently observed for reverse osmosis systems; other POU devices had variable effects on arsenic concentrations. These results indicate that while a single residential arsenic measurement may be used to represent exposure in this region, researchers must obtain information on changes in water source and POU treatment devices to better characterize population exposures over time.     

Relationship between persistent organic pollutants (POPs) and ranging patterns in common bottlenose dolphins (Tursiops truncatus) from coastal Georgia, USA

Bottlenose dolphins (Tursiops truncatus) are apex predators in coastal southeastern U.S. waters; as such they are indicators of persistent organic pollutants (POPs) in coastal ecosystems. POP concentrations measured in a dolphin's blubber are influenced by a number of factors, including the animal's sex and ranging pattern in relation to POP point sources. This study examined POP concentrations measured in bottlenose dolphin blubber samples (n = 102) from the Georgia, USA coast in relation to individual ranging patterns and specifically, distance of sightings from a polychlorinated biphenyl (PCB) point source near Brunswick, Georgia. Dolphin ranging patterns were determined based upon 5 years of photo-identification data from two field sites approximately 40 km apart: (1) the Brunswick field site, which included the Turtle/Brunswick River Estuary (TBRE), and (2) the Sapelo field site, which included the Sapelo Island National Estuarine Research Reserve (SINERR). Dolphins were categorized into one of three ranging patterns from photo-identification data. Individuals with sighting histories exclusively within one of the defined field sites were considered to have either Brunswick or Sapelo ranging patterns. Individuals sighted in both field sites were classified as having a Mixed ranging pattern. Brunswick males had the highest concentrations of PCBs reported for any marine mammal. The pattern of PCB congeners was consistent with Aroclor 1268, a highly chlorinated PCB mixture associated with a Superfund site in Brunswick. PCB levels in Sapelo males were lower than in Brunswick males, but comparable to the highest levels measured in other dolphin populations along the southeastern U.S. Female dolphins had higher Aroclor 1268 proportions than males, suggesting that the highly chlorinated congeners associated with Aroclor 1268 may not be offloaded through parturition and lactation, as easily as less halogenated POPs. Individuals sighted farther from the Superfund point source had lower Aroclor 1268 proportions.     

Long-range effect of cyanide on mercury methylation in a gold mining area in southern Ecuador

Small-scale gold mining in Portovelo-Zaruma, Southern Equador, performed by mercury amalgamation and cyanidation, yields 9-10 t of gold/annum, resulting in annual releases of around 0.65 t of inorganic mercury and 6000 t of sodium cyanide in the local river system. The release of sediments, cyanide, mercury, and other metals present in the ore such as lead, manganese and arsenic significantly reduces biodiversity downstream the processing plants and enriches metals in bottom sediments and biota. However, methylmercury concentrations in sediments downstream the mining area were recently found to be one order of magnitude lower than upstream or in small tributaries. In this study we investigated cyanide, bacterial activity in water and sediment and mercury methylation potentials in sediments along the Puyango river watershed, measured respectively by in-situ spectrophotometry and incubation with ³H-leucine and ²⁰³Hg²⁺.Free cyanide was undetectable (< 1 μg·L^− 1) upstream mining activities, reached 280 μg·L^− 1 a few km downstream the processing plants area and was still detectable about 100 km downstream. At stations with detectable free cyanide in unfiltered water, 50% of it was dissolved and 50% associated to suspended particles. Bacterial activity and mercury methylation in sediment showed a similar spatial pattern, inverse to the one found for free cyanide in water, i.e. with significant values in pristine upstream sampling points (respectively 6.4 to 22 μgC·mg wet weight^− 1·h^− 1 and 1.2 to 19% of total ²⁰³Hg·g dry weight^− 1·day^− 1) and undetectable downstream the processing plants, returning to upstream values only in the most distant downstream stations. The data suggest that free cyanide oxidation was slower than would be expected from the high water turbulence, resulting in a long-range inhibition of bacterial activity and hence mercury methylation. The important mercury fluxes resultant from mining activities raise concerns about its biomethylation in coastal areas where many mangrove areas have been converted to shrimp farming.