Mobilization of soil organic matter by complexing agents and implications for polycyclic aromatic hydrocarbon desorption

Complexing agents are frequently used in treatment technologies to remediate soils, sediments and wastes contaminated with toxic metals. The present study reports results that indicate that the rate and extent of soil organic matter (SOM) as represented by dissolved natural organic carbon (DNOC) and polycyclic aromatic hydrocarbon (PAH) desorption from a contaminated soil from a manufactured gas plant (MGP) site can be significantly enhanced with the aid of complexing agents. Desorption of DNOC and PAH compounds was pH dependent, with minimal release occurring at pH 2-3 and maximal release at pH 7-8. At pH-6, chelate solutions were shown to dissolve large amounts of humic substances from the soil compared to controls. The complexing agents mobilized polyvalent metal ions, particularly Fe and Al from the soil. Metal ion chelation may disrupt humic (metal ion)-mineral linkages, resulting in mobilization of SOM and accompanying PAH molecules into the aqueous phase; and/or reduce the degree of cross-linking in the soil organic matter phase, which could accelerate PAH diffusion.     

Radium-226 in water, sediments, and fish from lakes near the city of Elliot Lake, Ontario, Canada

Ra-226 was measured by alpha-emission spectroscopy in water, sediments, and fish (tissues and gut contents), from five lakes in a watershed containing U mining and milling operations at Elliot Lake, Ontario, and from control lakes in an adjacent non-industrialized watershed. Ra-226 transfer parameters from lake water and sediments to fish tissues, and annual intakes by humans consuming fish, were estimated. Mean dissolved 226Ra levels ranged from approximately 76 mBq litre(-1) in water of the most affected lake, to < 10 mBq litre(-1) in control lakes. Levels in summer were consistently higher than in fall or winter; no consistent variation with depth was noted. Sediment levels ranged from approximately 3000 mBq g(-1) dry wt in one study lake to < 100 mBq g(-1) dry wt of sediment in control lakes. Bone 226Ra concentrations were higher than in muscle. The lake trout (Salvelinus namaycush), a predatory secondary consumer, had bone 226Ra levels (< 20 mBq g(-1) dry wt) that did not show significant site variation. In contrast, bottom feeding whitefish had significantly more 226Ra in bone tissue (to 38 mBq g(-1) dry wt in the lake whitefish, Coregonus clupeaformis, and 76 mBq g(-1) in round whitefish, Prosopium cylindraceum) in study lakes than in controls (< 20 mBq g(-1) dry wt). Ra-226 levels in lake trout muscle were low and showed erratic variation among lakes whereas levels in whitefish muscle did not vary significantly among study and control sites. Lake herring (= cisco, Coregonus artedii), a planktivorous fish taken only from Quirke Lake, had mean 226Ra levels of 18 and 1.4 mBq g(-1) dry wt in bone and muscle, respectively. Gut 226Ra levels, highest in lake trout from McCabe and Quirke Lakes (126 +/- 53, 64 +/- 44 mBq g(-1) dry wt, respectively), and just detectable in McCabe and Elliot Lake whitefish (24 +/- 2, 36 +/- 14 mBq g(-1) dry wt, respectively), were below detection in lake trout and whitefish from other lakes. Concentration ratios (CRs) of 226Ra from water to muscle ranged from 8 to 14 in lake trout, 7 to 14 in whitefish, and 4 to 6 in lake herring. The water to bone CRs varied from 81 to 142, 314 to 548, and 126 to 272 in the same species. CRs were always < 1 between sediments and fish tissues. Annual intake of 226Ra by human consumers of these fish was estimated to provide an effective dose of 0.003 mSv year(-1). This represents a small fraction of both natural background (> 2 mSv year(-1)) and the public dose limit (5 mSv year(-1)).     

U- and Th-series radionuclides in snowshoe hare (Lepus americanus) taken near U mill tailings close to Elliot Lake, Ontario, Canada

Snowshoe hare (Lepus americanus) trapped near U tailings had higher concentrations of (226)Ra in their bones (250 +/- 94 mBq g(-1) dry wt) than those from local control sites 3-15 km from the tailings (20-30 mBq g(-1) dry wt) and those from a distant control site 880 km away from the U mining area, which were below the detection limit (DL) (3.7 mBq g(-1) dry wt). Most chyme (stomach content) samples contained 226Ra below DL. Concentration ratios of 226Ra from tissues of local plants, considered important in the hare's diet, to bone ranged from 0.22 to 8.60. Concentrations of 210Pb and 210Po (95-245 mBq g(-1) dry wt) were not significantly different among tailings and control site populations. Disequilibrium between these isotopes and their precursors was noted. No significant accumulation of U and Th was noted at any site. Higher concentrations of 228Th compared to 232Th are attributed to accumulation of 228Ra in a manner similar to that of 226Ra. Based on bone 226Ra and 210Po contents, the maximum internal dose rates to the skeleton and the maximum life-time dose of hare living near tailings were 3.9 x 10(-5) Gy d(-1) and 4.2 x 10(-2) Gy, respectively. These rates were below the threshold required to produce osteosarcoma in other mammals and were considered unlikely to adversely affect hare during their lifetime. Radionuclide uptake by the animals was concluded to have no environmental significance in the transport of radionuclides from tailings to other locations.     

Kinetics of mass and DNA decomposition in tomato leaves

This laboratory study investigated the kinetics of leaf and DNA content decomposition in two varieties of tomato (Palmiro and Admiro) after incubation in soil for 35 days. Results revealed that the decrease of dry matter in leaves in both varieties did not follow a single exponential function and was better described by a double exponential model. Composite half-decrease times were 3.4 and 2.4 days for Palmiro and Admiro respectively. The same pattern was observed for DNA mass loss, although this was closer to a single exponential model with composite half-decrease times of 1.5 and 1.4 days. Genomic analysis showed that DNA in dried leaves at room temperature (not inoculated in the soil), remains intact or presents a weak degradation, and DNA extracted from leaves inoculated in non-sterile soil showed degradation after two days. These results indicate that before release an important quantity of DNA may be degraded inside plant tissues during decomposition in soil.     

Electrochemical monitoring of methylparathion degradation in an acid aqueous medium in presence of Cu(II)

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o,4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2-7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH < or = 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 x 10(-3) s(-1) at pH 2, 5.5 x 10(-3) s(-1) at pH 4 and 9.0 x 10(-3) s(-1) at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Assessing the effect of climate oscillations and land-use changes on streamflow in the central Spanish Pyrenees

Plans to increase the amount of irrigated land in Mediterranean countries should consider how changes in climate and land-use affect water resources. In this study, both precipitation and temperature were used to analyze regional trends in discharge in the basins of the Central Spanish Pyrenees since the mid-20th century. Annual variations in the relationship between precipitation and discharge suggested that discharge was relatively lower in the second half of the study period, coinciding with major changes in land use. On a monthly scale, precipitation increased significantly in October, April, and July, and decreased in March, and temperature increased in January and February and decreased in April. Nevertheless, discharge has decreased significantly in most months in the past 50 years. Land-use and plant-cover changes are the only nonclimatic factor that can explain the loss of around 30% of the average annual discharge.     

Bioavailability and biodegradation of prosulfocarb in soil

Active microbial degraders of the herbicide prosulfocarb (PSC) were isolated to evaluate their performance in soil with a view to their use for bioremediation. The isolated cultures (a microbial consortium and a Pseudomonas sp. strain) were active when tested in mineral medium with PSC as the only carbon source, but had an adverse effect on the soil indigenous microflora. Biodegradation in the inoculated soils was thus lower than in the uninoculated soil when only the indigenous microflora was present. Further tests showed that the strong affinity of PSC for soil organic matter affected its bioavailability and hence its biodegradation by the inocula. Bioremediation of PSC contaminated soils could thus be undertaken by biostimulation of indigenous microflora.     

Radium-226 in cattails, Typha latifolia, and bone of muskrat, Ondatra zibethica (L.), from a watershed with uranium tailings near the city of Elliot Lake, Canada

Radium-226 concentrations were measured in the main food plants (cattails, Typha latifolia) and bone of adult muskrats (Ondatra zibethica (L.)), taken from a study area near Quirke Lake in the Serpent River drainage basin. This watershed receives drainage containing radionuclides from the U tailings near the City of Elliot Lake, Ontario, Canada. Two control sites (one local, one 130 km distant) were also sampled. Radium-226 levels in cattails varied by plant part and place of collection. Roots sampled in the study area had the highest mean (226)Ra level (1135.0 mBq g(-1)), stems and leaves had 284.2 and 275.9 mBq g(-1), respectively (dry-weight basis, n = 6 in all cases). Local and distant control cattails carried much lower (226)Ra levels (20.2 and 15.2 mBq g(-1) dry weight, respectively, using pooled equal portions of all plant parts, n = 3 in both cases). Muskrats from waters with mean total (226)Ra levels in the period, 1984-1987 greater than 75.0 mBq litre(-1) ('study-high' sites), near U tailings within 10 km of Quirke Lake, had a mean (geometric) bone level of (226)Ra of 344.9 mBq g(-1) (dry-weight basis, n = 36); those from nearby waters, containing < 75.0 mBq litre(-1) of (226)Ra ('study-low' sites), had a mean bone level (80.3 mBq g(-1), n = 9) similar to animals taken in unaffected local control areas 20 km from the tailings (79.1 mBq g(-1), n = 12); animals from the distant control area, near Sudbury, Ontario, had the lowest mean burden (11.5 mBq g(-1), n = 24). Levels were unrelated to age or sex of the animals. Dry-weight based (226)Ra concentration ratios (bone concentration/plant tissue concentration) were calculated to range from 0.3-1.4 in the study-high area to 2.4-6.3 in the local control area. Wet-weight based concentration ratios were about 4.3 times higher. Concentration ratios were similar to values calculated for other species and in general agreement with values calculated for humans. The muskrat is judged to be a useful indicator (biomonitor) of environmental (226)Ra levels as there is a highly significant positive correlation coefficient (r = 0.74) between bone and ambient (water) concentrations of the radionuclide (F79 = 95.04, P < 0.0001) Estimated yearly (226)Ra intake by people eating muskrats was calculated to be below the current allowable level set by Canadian regulatory authorities.     

Temperature dependence of Henry's law constants of metolachlor and diazinon

A dynamic system based on the water/air equilibrium at the interface within the length of a microporous tube has been used to determine experimentally the Henry's law constants (HLC) of two pesticides: metolachlor and diazinon. The measurements were conducted over the temperature range 283-301 K. At 293 K, HLCs values are (42.6+/-2.8) x 10(3) (in units of M atm(-1)) for metolachlor and (3.0+/-0.3)x10(3) for diazinon. The obtained data were used to derive the following Arrhenius expressions: HLC=(3.0+/-0.4) x 10(-11) exp((10,200+/-1,000)/T) for metolachlor and (7.2+/-0.5) x 10(-15) exp((11,900+/-700)/T) for diazinon. At a cumulus cloud temperature of 283 K, the fractions of metolachlor and diazinon in the atmospheric aqueous phase are about 57% and 11% respectively. In order to evaluate the impact of a cloud on the atmospheric chemistry of both studied pesticides, we compare also their atmospheric lifetimes under clear sky (tau(gas)), and cloudy conditions (tau(multiphase)). The calculated multiphase lifetimes (in units of hours) are significantly lower than those in gas phase at a cumulus temperature of 283 K (in parentheses): metolachlor, 0.4 (2.9); diazinon, 1.9 (5.0).     

Degradation of chlorobenzenes by a strain of Acidovorax avenae isolated from a polluted aquifer

A subsurface microbial community was isolated from a polluted site of Suquía River (Córdoba-Argentina), acclimated during 15 days in aerobic conditions using 1,2-dichlorobenzene (1,2-DCB) as the sole carbon source. From this acclimated community, we isolated and identified by 16S rDNA analysis a strain of Acidovorax avenae, which was able to perform the complete biodegradation of 1,2-DCB in two days affording stoichiometric amounts of chloride. This pure strain was also tested for biodegradation of chlorobenzene (CB); 1,3-DCB and 1,4-DCB, giving similar results to the experiments using 1,2-DCB. The aromatic-ring-hydroxylating dioxygenase (ARHDO) alpha-subunit gene core, encoding the catalytic site of the large subunit of chlorobenzene dioxygenase, was detected by PCR amplification and confirmed by DNA sequencing. These results suggest that the isolated strain of A. avenae could use a catabolic pathway, via ARHDO system, leading to the formation of chlorocatecols during the first steps of biodegradation, with further chloride release and subsequent paths that showed complete substrate consumption.