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.     

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.     

Simple models for phosphorus loss from manure during rainfall

Mechanistic, predictive equations for phosphorus (P) transport in runoff from manure-applied fields constitute a critical knowledge gap for developing nonpoint-source pollution models. We derived two simple equations to describe the P release from animal manure during a rainfall event-one based on first-order P desorption kinetics and one based on second-order kinetics. The manure characteristics needed in the two kinetic equations are the maximum amount of water-extractable phosphorus (WEP) and a characteristic desorption time. Water-extractable P can be measured directly but currently the characteristic time can only be obtained by fitting experimental data. In addition, we evaluated two models usually used to estimate P loss from soil, the Elovitch equation and power function, both of which relate P loss to time. The models were tested against previously published data of P release from different manures under laboratory conditions. All equations fit the data well. Of the two kinetic equations, the second-order model showed better agreement with the data than the first-order model; for example, maximum relative differences between the model results and measured data were 2.6 and 4.7%, respectively. The characteristic times varied between 20 min for dairy manure and almost 100 min for poultry manure. The characteristic time did not appear to change with flow rate but decreased with smaller manure aggregates. The parameters for power-function relationships could not be related to measured manure characteristics. These results provide the first step to process-based approximations for predicting P release from manure with time during rainfall shortly after land application, when P losses are the greatest.     

The acetochlor registration partnership surface water monitoring program for four corn herbicides

A surface drinking water monitoring program for four corn (Zea mays L.) herbicides was conducted during 1995-2001. Stratified random sampling was used to select 175 community water systems (CWSs) within a 12-state area, with an emphasis on the most vulnerable sites, based on corn intensity and watershed size. Finished drinking water was monitored at all sites, and raw water was monitored at many sites using activated carbon, which was shown capable of removing herbicides and their degradates from drinking water. Samples were collected biweekly from mid-March through the end of August, and twice during the off-season. The analytical method had a detection limit of 0.05 microg L(-1) for alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)-acetamide] and 0.03 microg L(-1) for acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide], atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine], and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide]. Of the 16528 drinking water samples analyzed, acetochlor, alachlor, atrazine, and metolachlor were detected in 19, 7, 87, and 53% of the samples, respectively. During 1999-2001, samples were also analyzed for the presence of six major degradates of the chloroacetanilide herbicides, which were detected more frequently than their parent compounds, despite having higher detection limits of 0.1 to 0.2 microg L(-1). Overall detection frequencies were correlated with product use and environmental fate characteristics. Reservoirs were particularly vulnerable to atrazine, which exceeded its 3 microg L(-1) maximum contaminant level at 25 such sites during 1995-1999. Acetochlor annualized mean concentrations (AMCs) did not exceed its mitigation trigger (2 microg L(-1)) at any site, and comparisons of observed levels with standard measures of human and ecological hazards indicate that it poses no significant risk to human health or the environment.     

WATER QUALITY IMPROVEMENT PROGRAM EFFECTIVENESS FOR CARBONATE AQUIFERS IN GRAZED LAND WATERSHEDS1

ABSTRACT: Water quality indicators of two agriculturally impacted karst areas in southeastern West Virginia were studied to determine the water quality effects of grazing agriculture and water quality trends following initiation of water quality improvement programs. Both areas are tributaries of the Greenbrier River and received funding for best management practices under the President's Initiative for Water Quality and then under the Environmental Quality Incentives Program (EQIP). After 11 years of study there was little evidence to suggest that water quality improved in one area. Three and a half years of study in the other area showed little evidence of consistent water quality improvement under EQIP. Lack of consistent water quality improvement at the catchment scale does not imply that the voluntary programs were failures. Increased livestock numbers as a result of successful changes in forage management practices may have overridden water quality improvements achieved through best management practices. Practices that target well defined contributing areas significantly impacting aquifer water quality might be one way to improve water quality at catchment scales in karst basins. For example, a significant decrease in fecal coliform concentrations was observed in subterranean drainage from one targeted sinkhole after dairy cattle were permanently excluded from the sinkhole.     

SUMMER LOW FLOWS IN NEW ENGLAND DURING THE 20TH CENTURY1

ABSTRACT: High springtime river flows came earlier by one to two weeks in large parts of northern New England during the 20th Century. In this study it was hypothesized that late spring/early summer recessional flows and late summer/early fall low flows could also be occurring earlier. This could result in a longer period of low flow recession and a decrease in the magnitude of low flows. To test this hypothesis, variations over time in the magnitude and timing of low flows were analyzed. To help understand the relation between low flows and climatic variables in New England, low flows were correlated with air temperatures and precipitation. Analysis of data from 23 rural, unregulated rivers across New England indicated little evidence of consistent changes in the timing or magnitude of late summer/early fall low flows during the 20th Century. The interannual variability in the timing and magnitude of the low flows in northern New England was explained much more by the interannual variability in precipitation than by the interannual variability of air temperatures. The highest correlation between the magnitude of the low flows and air temperatures was with May through November temperatures (r =?0.37, p= 0.0017), while the highest correlation with precipitation was with July through August precipitation (r = 0.67, p > 0.0001).     

MODELING THE DISTRIBUTION OF DIFFUSE NITROGEN SOURCES AND SINKS IN THE NEUSE RIVER BASIN OF NORTH CAROLINA,USA1

This study quantified nonpoint source nitrogen (NPS‐N) sources and sinks across the 14,582 km² Neuse River Basin (NRB) located in North Carolina, to provide tabular data summaries and graphic overlay products to support the development of management approaches to best achieve established N reduction goals. First, a remote sensor derived, land cover classification was performed to support modeling needs. Modeling efforts included the development of a mass balance model to quantify potential N sources and sinks, followed by a precipitation event driven hydrologic model to effectively transport excess N across the landscape to individual stream reaches to support subsequent labeling of transported N values corresponding to source origin. Results indicated that agricultural land contributed 55 percent of the total annual NPS‐N loadings, followed by forested land at 23 percent (background), and urban areas at 21 percent. Average annual N source contributions were quantified for agricultural (1.4 kg/ha), urban (1.2 kg/ha), and forested cover types (0.5 kg/ha). Nonpoint source‐N contributions were greatest during the winter (40 percent), followed by spring (32 percent), summer (28 percent), and fall (0.3 percent). Seasonal total N loadings shifted from urban dominated and forest dominated sources during the winter, to agricultural sources in the spring and summer. A quantitative assessment of the significant NRB land use activities indicated that high (greater than 70 percent impervious) and medium (greater than 35 percent impervious) density urban development were the greatest contributors of NPS‐N on a unit area basis (1.9 and 1.6 kg/ha/yr, respectively), followed by row crops and pasture/hay cover types (1.4 kg/ha/yr).