Equilibrium and kinetic studies on biosorption of Hg(II), Cd(II) and Pb(II) ions onto microalgae Chlamydomonas reinhardtii

The microalgae Chlamydomonas reinhardtii was used for the biosorption of Hg(II), Cd(II) and Pb(II) ions. The maximum adsorption of Hg(II) and Cd(II) ions on Chlamydomonas reinhardtii biomass was observed at pH 6.0 and the corresponding value for Pb(II) ions was 5.0. The biosorption of Hg(II), Cd(II) and Pb(II) ions by microalgae biomass increased as the initial concentration of Hg(II), Cd(II) and Pb(II) ions increased in the biosorption medium. The maximum biosorption capacities of microalgae for Hg(II), Cd(II) and Pb(II) ions were 72.2+/-0.67, 42.6+/-0.54 and 96.3+/-0.86 mg/g dry biomass, respectively. The affinity order for algal biomass was Pb(II)>Hg(II)>Cd(II). FT-IR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which were responsible for biosorption of metal ions. Biosorption equilibrium was established in about 60 min and the equilibrium was well described by the Freundlich biosorption isotherms. Temperature change in the range of 5-35 degrees C did not affect the biosorption capacity. The microalgae could be regenerated using 0.1 M HCl, with up to 98% recovery, which allowed the reuse of the biomass in six biosorption-desorption cycles without any considerable loss of biosorption capacity.     

The effect of Na and Ca salts on MSWI bottom ash activation for reuse as a pozzolanic admixture

In this study the possibility of both chemical and combined chemical + thermal activation of municipal solid waste incinerator bottom ash was investigated. A number of chemical activators including Na₂SiO₃·9H₂O, NaOH, Na₂SO₄ and CaCl₂·2H₂O were individually added at varying concentrations to bottom ash/Portland cement mixtures having different bottom ash contents. The effect of the selected compounds was evaluated in terms of macroscopic properties including mechanical strength and composition of cementitious materials/water slurries. The results showed that Na-based activators were not capable of improving the characteristics of the cementitious products if compared to Portland cement under both normal and accelerated curing. Conversely, the use of calcium chloride at 40 °C-curing did promote the pozzolanic properties of bottom ash, leading to UCS values of 45.5 and 60.0 MPa after 10 and 20 days, respectively, as opposed to a value of 43.6 MPa obtained after 28 days for Portland cement under normal curing conditions.     

In situ measurements of nitrate leaching implicate poor nitrogen and irrigation management on sandy soils

Minimizing the risk of nitrate contamination along the waterways of the U.S. Great Plains is essential to continued irrigated corn production and quality water supplies. The objectives of this study were to quantify nitrate (NO(3)) leaching for irrigated sandy soils (Pratt loamy fine sand [sandy, mixed, mesic Lamellic Haplustalfs]) and to evaluate the effects of N fertilizer and irrigation management strategies on NO(3) leaching in irrigated corn. Two irrigation schedules (1.0x and 1.25x optimum) were combined with six N fertilizer treatments broadcast as NH(4)NO(3) (kg N ha(-1)): 300 and 250 applied pre-plant; 250 applied pre-plant and sidedress; 185 applied pre-plant and sidedress; 125 applied pre-plant and sidedress; and 0. Porous-cup tensiometers and solution samplers were installed in each of the four highest N treatments. Soil solution samples were collected during the 2001 and 2002 growing seasons. Maximum corn grain yield was achieved with 125 or 185 kg N ha(-1), regardless of the irrigation schedule (IS). The 1.25x IS exacerbated the amount of NO(3) leached below the 152-cm depth in the preplant N treatments, with a mean of 146 kg N ha(-1) for the 250 and 300 kg N preplant applications compared with 12 kg N ha(-1) for the same N treatments and 1.0x IS. With 185 kg N ha(-1), the 1.25x IS treatment resulted in 74 kg N ha(-1) leached compared with 10 kg N ha(-1) for the 1.0x IS. Appropriate irrigation scheduling and N fertilizer rates are essential to improving N management practices on these sandy soils.     

Evaluation of simplifying assumptions on pesticide degradation in soil

There is evidence that degradation of pesticides in simple laboratory systems may differ from that in the field, but it is not clear which of the simplifications inherent in laboratory studies present serious shortcomings. Laboratory experiments evaluated several simplifying assumptions for a clay loam soil and contrasting pesticides. Degradation of cyanazine [2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropiononitrile] and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide] at fluctuating temperature and moisture was predicted reasonably well based on parameters derived from degradation under constant conditions. There was a tendency for slower degradation of cyanazine and bentazone in soil aggregates of 3 to 5 mm in diameter (DT50 at 15 degrees C and 40% maximum water holding capacity of 25.1 and 58.2 d, where DT50 is the time for 50% decline of the initial pesticide concentration) than in soil sieved to <3 mm (DT50 of 19.1 and 37.6 d), but the differences were not significant for most datasets. Degradation of cyanazine, isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea], and chlorotoluron [3-(3-chloro-p-tolyl)-1,1-dimethylurea] was measured in soil amended with different amounts of lignin. The effect of lignin on degradation was small despite considerable differences in sorption. The DT50 values of cyanazine, isoproturon, and chlorotoluron were 16.2, 18.6, and 33.0 d, respectively, in soil without lignin and 19.0, 23.4, and 34.6 d, respectively, in soil amended with 2% lignin. Degradation of bentazone and cyanazine in repacked soil columns was similar under static and flow conditions with 50.1 and 47.2% of applied bentazone and 74.7 and 73.6% of applied cyanazine, respectively, degraded within 20 d of application. Thus, the assumptions underpinning laboratory to field extrapolation tested here were considered to hold for our experimental system. Additional work is required before general conclusions can be drawn.     

An alum-based water treatment residual can reduce extractable phosphorus concentrations in three phosphorus-enriched coastal plain soils

The accumulation of excess soil phosphorus (P) in watersheds under intensive animal production has been linked to increases in dissolved P concentrations in rivers and streams draining these watersheds. Reductions in water dissolved P concentrations through very strong P sorption reactions may be obtainable after land application of alum-based drinking water treatment residuals (WTRs). Our objectives were to (i) evaluate the ability of an alum-based WTR to reduce Mehlich-3 phosphorus (M3P) and water-soluble phosphorus (WSP) concentrations in three P-enriched Coastal Plain soils, (ii) estimate WTR application rates necessary to lower soil M3P levels to a target 150 mg kg(-1) soil M3P concentration threshold level, and (iii) determine the effects on soil pH and electrical conductivity (EC). Three soils containing elevated M3P (145-371 mg kg(-1)) and WSP (12.3-23.5 mg kg(-1)) concentrations were laboratory incubated with between 0 and 6% WTR (w w(-1)) for 84 d. Incorporation of WTR into the three soils caused a near linear and significant reduction in soil M3P and WSP concentrations. In two soils, 6% WTR application caused a soil M3P concentration decrease to below the soil P threshold level. An additional incubation on the third soil using higher WTR to soil treatments (10-15%) was required to reduce the mean soil M3P concentration to 178 mg kg(-1). After incubation, most treatments had less than a half pH unit decline and a slight increase in soil EC values suggesting a minimal impact on soil quality properties. The results showed that WTR incorporation into soils with high P concentrations caused larger relative reductions in extractable WSP than M3P concentrations. The larger relative reductions in the extractable WSP fraction suggest that WTR can be more effective at reducing potential runoff P losses than usage as an amendment to lower M3P concentrations.     

Runoff phosphorus losses from surface-applied biosolids

Runoff losses of dissolved and particulate phosphorus (P) may occur when rainfall interacts with manures and biosolids spread on the soil surface. This study compared P levels in runoff losses from soils amended with several P sources, including 10 different biosolids and dairy manure (untreated and treated with Fe or Al salts). Simulated rainfall (71 mm h(-1)) was applied until 30 min of runoff was collected from soil boxes (100 x 20 x 5 cm) to which the P sources were surfaced applied. Materials were applied to achieve a common plant available nitrogen (PAN) rate of 134 kg PAN ha(-1), resulting in total P loading rates from 122 (dairy manure) to 555 (Syracuse N-Viro biosolids) kg P ha(-1). Two biosolids produced via biological phosphorus removal (BPR) wastewater treatment resulted in the highest total dissolved phosphorus (13-21.5 mg TDP L(-1)) and total phosphorus (18-27.5 mg TP L(-1)) concentrations in runoff, followed by untreated dairy manure that had statistically (p = 0.05) higher TDP (8.5 mg L(-1)) and TP (10.9 mg L(-1)) than seven of the eight other biosolids. The TDP and TP in runoff from six biosolids did not differ significantly from unamended control (0.03 mg TDP L(-1); 0.95 mg TP L(-1)). Highest runoff TDP was associated with P sources low in Al and Fe. Amending dairy manure with Al and Fe salts at 1:1 metal-to-P molar ratio reduced runoff TP to control levels. Runoff TDP and TP were not positively correlated to TP application rate unless modified by a weighting factor reflecting the relative solubility of the P source. This suggests site assessment indices should account for the differential solubility of the applied P source to accurately predict the risk of P loss from the wide variety of biosolids materials routinely land applied.     

Polycyclic aromatic hydrocarbons (PAHs) in soils of the Moscow Region--concentrations, temporal trends, and small-scale distribution

The knowledge of the environmental fate of polycyclic aromatic hydrocarbons (PAHs) is restricted to few climatic regions of the world almost excluding the Taiga. Our objectives were to (i) separate anthropogenic from background contributions to PAH concentrations and (ii) determine temporal trends in PAH concentrations during the last century including the change in distribution of PAHs in interior and exterior portions of aggregates in soils of the Moscow region. Along a southeast-bound transect from Moscow (windward in winter) and at a background location northeast of Moscow (leeward in winter), seven topsoil samples were collected in 1910-1954 and 35 in 1998-2003. We fractionated the soils in interior and exterior portions of aggregates > 10 mm and remaining soil without aggregates. The sum of 21 PAHs (sigma21PAHs) concentrations in recent bulk soil ranged from 59 to 1350 ng g(-1). The concentrations of all PAHs were lower outside than in Moscow. The range of the concentrations of the sigma21PAHs in archived soil samples (159-1280 ng g(-1)) was similar as in recent soils. In most recent and archived samples, naphthalene and phenanthrene, were most abundant. The concentrations of low-molecular-weight PAHs decreased during the last century at most sites; those of high-molecular-weight compounds increased. The sigma21PAHs concentrations were accumulated in the exterior of aggregates (109%) and depleted in the interior (95%) relative to the concentration in bulk soil (defined as 100%), which was similar to that in the soil without aggregates (99%). The differences between aggregate interior and exterior did not change during the last century. The dominance of naphthalene and phenanthrene is typical of remote regions. The urban influence on PAH concentrations in the last century was small.     

Effects of commercial diazinon and imidacloprid on microbial urease activity in soil and sod

Diazinon [O,O-diethyl O-2-isopropyl-6-methyl(pyrimidine-4-yl) phosphorothioate] and imidacloprid [1-(1-[6-chloro-3-pyridinyl]methyl)-N-nitro-2-imidazolidinimine] are applied to lawns for insect control simultaneously with nitrogenous fertilizers such as urea, but their potential effect on urease activity and nitrogen availability in turfgrass management has not been evaluated. Urease activity in enzyme assays, washed cell assays, and soil slurries was examined as a function of insecticide concentration. Intact cores from field sites were used to assess the effect of insecticide application on urease activity in creeping bentgrass (Agrostis palustris Huds.) and bluegrass (Poa pratensis L.) sod. Bacterial urease from Bacillus pasteurii and plant urease from jack bean [Canavalia ensiformis (L.) DC.] were unaffected by the insecticides. Both insecticides inhibited the growth of Proteus vulgaris, a urease-producing bacterium, but only diazinon significantly reduced urease activity in washed cells; neither insecticide inhibited urease activity in sonicated cells. Neither diazinon nor imidacloprid inhibited urease activity in Woolper soil (fine, mixed, mesic Typic Argiudoll) slurries, but diazinon slightly inhibited urease activity in Maury soil (fine, mixed, semiactive, mesic Typic Paleudalf) slurries. Imidacloprid had no effect on urease activity in creeping bentgrass or bluegrass sod at up to 10 times the commercial application rate. Diazinon briefly, but significantly, reduced urease activity in bluegrass sod. Co-application of imidacloprid and urea appears to be benign with respect to urease activity in soil and sod. Diazinon, in contrast, appears to have a significant, short-term, inhibitory effect on the microbial urease-producing community, but that effect depends on soil type.     

Green roof stormwater retention: effects of roof surface, slope, and media depth

Urban areas generate considerably more stormwater runoff than natural areas of the same size due to a greater percentage of impervious surfaces that impede water infiltration. Roof surfaces account for a large portion of this impervious cover. Establishing vegetation on rooftops, known as green roofs, is one method of recovering lost green space that can aid in mitigating stormwater runoff. Two studies were performed using several roof platforms to quantify the effects of various treatments on stormwater retention. The first study used three different roof surface treatments to quantify differences in stormwater retention of a standard commercial roof with gravel ballast, an extensive green roof system without vegetation, and a typical extensive green roof with vegetation. Overall, mean percent rainfall retention ranged from 48.7% (gravel) to 82.8% (vegetated). The second study tested the influence of roof slope (2 and 6.5%) and green roof media depth (2.5, 4.0, and 6.0 cm) on stormwater retention. For all combined rain events, platforms at 2% slope with a 4-cm media depth had the greatest mean retention, 87%, although the difference from the other treatments was minimal. The combination of reduced slope and deeper media clearly reduced the total quantity of runoff. For both studies, vegetated green roof systems not only reduced the amount of stormwater runoff, they also extended its duration over a period of time beyond the actual rain event.     

Macroinvertebrate communities in agriculturally impacted southern Illinois streams: patterns with riparian vegetation, water quality, and in-stream habitat quality

Relationships between riparian land cover, in-stream habitat, water chemistry, and macroinvertebrates were examined in headwater streams draining an agricultural region of Illinois. Macroinvertebrates and organic matter were collected monthly for one year from three intensively monitored streams with a gradient of riparian forest cover (6, 22, and 31% of riparian area). Bioassessments and physical habitat analyses were also performed in these three streams and 12 other nearby headwater streams. The intensively monitored site with the least riparian forest cover had significantly greater percent silt substrates than the sites with medium and high forest cover, and significantly higher very fine organics in substrates than the medium and high forested sites. Macroinvertebrates were abundant in all streams, but communities reflected degraded conditions; noninsect groups, mostly oligochaetes and copepods, dominated density and oligochaetes and mollusks, mostly Sphaerium and Physella, dominated biomass. Of insects, dipterans, mostly Chironomidae, dominated density and dipterans and coleopterans were important contributors to biomass. Collector-gatherers dominated functional structure in all three intensively monitored sites, indicating that functional structure metrics may not be appropriate for assessing these systems. The intensively monitored site with lowest riparian forest cover had significantly greater macroinvertebrate density and biomass, but lowest insect density and biomass. Density and biomass of active collector-filterers (mostly Sphaerium) decreased with increasing riparian forest. Hilsenhoff scores from all 15 sites were significantly correlated with in-stream habitat scores, percent riparian forest, and orthophosphate concentrations, and multiple regression indicated that in-stream habitat was the primary factor influencing biotic integrity. Our results show that these "drainage ditches" harbor abundant macroinvertebrates that are typical of degraded conditions, but that they can reflect gradients of conditions in and around these streams.