Utilization of powdered waste sludge (PWS) for removal of textile dyestuffs from wastewater by adsorption

Acid pre-treated powdered waste sludge (PWS) was used for removal of textile dyestuffs from aqueous medium by adsorption as an alternative to the use of powdered activated carbon (PAC). The rate and extent of dysetuff removals were determined for four different dyestuffs at different PWS concentrations varying between 1 and 6 gl(-1). Biosorbed dyestuff concentrations at equilibrium decreased with increasing PWS concentration for all dyestuffs tested. PWS was more effective for adsorption of Remazol red RR and Chrisofonia direct yellow 12 as compared to the other dyestuffs tested. More than 80% percent dyestuff removal was obtained for all dyestuffs at PWS concentrations above 4 gl(-1) after 6h of incubation. Similar to percent dyestuff removal, the rate of adsorption was maximum at a PWS concentration of 4 gl(-1). Kinetics of adsorption of dyestuffs was investigated by using the first- and second-order kinetic models and the kinetic constants were determined. Second-order kinetics was found to fit the experimental data better than the first-order model for all dyestuffs tested. Adsorption isotherms were established for all dyestuffs used and the isotherm constants were determined by using the experimental data. Langmuir and the generalized adsorption isotherms were found to be more suitable than the Freundlich isotherm for correlation of equilibrium adsorption data. Acid pre-treated PWS was proven to be an effective adsorbent for dyestuff removal as compared to the other adsorbents reported in literature studies.     

Biological treatment of 2,4,6-trichlorophenol (TCP) containing wastewater in a hybrid bioreactor system with effluent recycle

Due to the toxic effects of trichlorophenol (TCP) on microorganisms, biological treatment efficiencies of TCP containing wastewaters are usually low. Synthetic wastewater containing 2,4,6-TCP was biologically treated in a hybrid-loop bioreactor system consisting of a packed column biofilm and an aerated tank bioreactor with effluent recycle in order to improve COD and TCP removals. Effects of the feed TCP concentration on COD, TCP and toxicity removal performance of the system were investigated for the feed TCP between 50 and 450 mg L(-1) while the sludge age (solids retention time, SRT) and hydraulic residence time (HRT) were kept constant at 20 d and 25 h, respectively. Biomass concentrations in the packed column and in the aeration tank decreased with increasing feed TCP concentrations due to toxic effects of TCP on the organisms. Low biomass concentrations in the system at high feed TCP contents resulted in low COD, TCP and toxicity removals. Therefore, percent TCP, COD and toxicity removals decreased with increasing feed TCP concentrations especially above 400 mg L(-1). The effluent TCP concentrations were lower than 20 mg L(-1) for the feed TCP concentrations below 390 mg L(-1) resulting in TCP and COD removals above 90%. Specific rates of TCP and COD removals increased with the feed TCP due to low biomass concentrations at high TCP contents. The system should be operated at a feed TCP lower than 400 mg L(-1) in order to obtain more than 90% TCP, COD and toxicity removals under the specified experimental conditions.     

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.     

Effects of feeding time and organic loading in an anaerobic sequencing batch biofilm reactor (ASBBR) treating diluted whey

An investigation was carried out on the performance of an anaerobic sequencing batch biofilm reactor (ASBBR) treating diluted cheese whey when submitted to different feed strategies and volumetric organic loads (VOL). Polyurethane foam cubes were used as support for biomass immobilization and stirring was provided by helix impellers. The reactor with a working volume of 3 L treated 2 L of wastewater in 8-h cycles at 500 rpm and 30 degrees C. The organic loads applied were 2, 4, 8 and 12 g COD L(-1) d(-1), obtained by increasing the feed concentration. Alkalinity was supplemented at a ratio of 50% NaHCO(3)/COD. For each organic load applied three feed strategies were tested: (a) batch operation with 8-h cycle; (b) 2-h fed-batch operation followed by 6-h batch; and (c) 4-h fed-batch followed by 4-h batch. The 2-h fed-batch operation followed by 6-h batch presented the best results for the organic loads of 2 and 4 g COD L(-1) d(-1), whereas the 4-h fed-batch operation followed by 4-h batch presented results slightly inferior for the same organic loads and the best results at organic loads of 8 and 12 g COD L(-1) d(-1). The concentration of total volatile acids varied with fill time. For the higher fill times maximum concentrations were obtained at the end of the cycle. Moreover, no significant difference was detected in the maximum concentration of total volatile acids for any of the investigated conditions. However, the maximum values of propionic acid tended to decrease with increasing fill time considering the same organic load. Microbiological analyses revealed the presence of Methanosaeta-like structures and methanogenic hydrogenotrophic-like fluorescent bacilli. No Methanosarcina-like structures were observed in the samples.     

Adsorption and transport of arsenic(V) in experimental subsurface systems

The adsorption and transport of As(V) in a heterogeneous, iron oxide-containing soil was investigated in batch and column laboratory experiments. The As(V) adsorbed rapidly to the soil over the first 48 h, but continued to adsorb slowly over the next several weeks, clearly indicating the potential for rate-limited transport. The equilibrium As(V) adsorption isotherm was markedly nonlinear, further indicating the potential for nonideal transport. A model developed for the adsorption of As(V) to hydrous ferric oxide (HFO) was able to predict the pH-dependent adsorption of As(V) to the soil in batch experiments within 0.116 to 0.726 root mean square error (RMSE). Arsenic(V) was significantly retarded in column transport experiments. The column transport experiments were modeled using the one-dimensional advection-dispersion equation, considering both linear and nonlinear adsorption equilibrium. Although the nonlinear local equilibrium model (NLLE, RMSE = 0.273) predicted the data better than the linear local equilibrium model (LLE, RMSE = 0.317), As(V) breakthrough occurred more rapidly than predicted by either model due to adsorption nonequilibrium. However, due to the presence of an irreversible or slowly desorbing fraction, the peak aqueous As(V) concentration (0.624 mg L(-1)) and the total amount of As(V) recovered (44%) was lower than predicted based on the two equilibrium models (NLLE and LLE). For the conditions used in this study [1 mg L(-1) As(V), pH 4.5 and 9,0-0.25 mM PO4, 0.53-1.6 cm min(-1) pore water velocity], the effect on As(V) mobility and recovery increased in the order pH < pore water velocity < PO4.     

Biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions by cross-linked metal-imprinted chitosans with epichlorohydrin

Cross-linked metal-imprinted chitosan microparticles were prepared from chitosan, using four metals (Cu(II), Zn(II), Ni(II), and Pb(II)) as templates, and epichlorohydrin as the cross-linker. The microparticles were characterized by Fourier transform infrared spectroscopy, solid state (13)C nuclear magnetic resonance spectroscopy, and energy-dispersive X-ray spectroscopy. They were used for comparative biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions in an aqueous solution. The results showed that the sorption capacities of Cu(II), Zn(II), Ni(II), and Pb(II) on the templated microparticles increased from 25 to 74%, 13 to 46%, 41 to 57%, and 12 to 43%, respectively, as compared to the microparticles without metal ion templates. The dynamic study showed that the sorption process followed the second-order kinetic equation. Three sorption models, Langmuir, Freundlich, and Dubinin-Radushkevich, were applied to the equilibrium isotherm data. The result showed that the Langmuir isotherm equation best fitted for monolayer sorption processes. Furthermore, the microparticles can be regenerated and reused for the metal removal.     

Kinetic of carbonaceous substrate in an upflow anaerobic sludge sludge blanket (UASB) reactor treating 2,4 dichlorophenol (2,4 DCP)

The performance of an upflow anaerobic sludge blanket (UASB) reactor treating 2,4 dichlorophenol (2,4 DCP) was evaluated at different hydraulic retention times (HRTs) using synthetic wastewater in order to obtain the growth substrate (glucose-COD) and 2,4 DCP removal kinetics. Treatment efficiencies of the UASB reactor were investigated at different hydraulic retention times (2-20 h) corresponding to a food to mass (F/M) ratio of 1.2-1.92 g-COD g(-1) VSS day(-1). A total of 65-83% COD removal efficiencies were obtained at HRTs of 2-20 h. In all, 83% and 99% 2,4 DCP removals were achieved at the same HRTs in the UASB reactor. Conventional Monod, Grau Second-order and Modified Stover-Kincannon models were applied to determine the substrate removal kinetics of the UASB reactor. The experimental data obtained from the kinetic models showed that the Monod kinetic model is more appropriate for correlating the substrate removals compared to the other models for the UASB reactor. The maximum specific substrate utilization rate (k) (mg-COD mg(-1) SS day(-1)), half-velocity concentration (K(s)) (mg COD l(-1)), growth yield coefficient (Y) (mg mg(-1)) and bacterial decay coefficient (b) (day(-1)) were 0.954 mg-COD mg(-1) SS day(-1), 560.29 mg-COD l(-1), 0.78 mg-SS g(-1)-COD, 0.093 day(-1) in the Conventional Monod kinetic model. The second-order kinetic coefficient (k(2)) was calculated as 0.26 day(-1) in the Grau reaction kinetic model. The maximum COD removal rate constant (U(max)) and saturation value (K(B)) were calculated as 7.502 mg CODl(-1)day(-1) and 34.56 mg l(-1)day(-1) in the Modified Stover-Kincannon Model. The (k)(mg-2,4 DCP mg(-1) SS day(-1)), (K(s)) (mg 2,4 DCPl(-1)), (Y) (mg SS mg(-1) 2,4 DCP) and (k(d)) (day(-1)) were 0.0041 mg-2,4 DCP mg(-1) SS day(-1), 2.06 mg-COD l(-1), 0.0017 mg-SS mg(-1) 2,4 DCP and 3.1 x 10(-5) day(-1) in the Conventional Monod kinetic model for 2,4 DCP degradation. The second-order kinetic coefficient (k(2)) was calculated as 0.30 day(-1) in the Grau reaction kinetic model. The maximum 2,4 DCP removal rate constant (U(max)) and saturation value (K(B)) were calculated as 0.01 mg COD l(-1) day(-1) and 9.8 x 10(-3) mg l(-1) day(-1) in the Modified Stover-Kincannon model.     

Biosorption of copper(II) and lead(II) onto potassium hydroxide treated pine cone powder

Pine cone powder surface was treated with potassium hydroxide and applied for copper(II) and lead(II) removal from solution. Isotherm experiments and desorption tests were conducted and kinetic analysis was performed with increasing temperatures.As solution pH increased, the biosorption capacity and the change in hydrogen ion concentration in solution increased. The change in hydrogen ion concentration for lead(II) biosorption was slightly higher than for copper(II) biosorption. The results revealed that ion-exchange is the main mechanism for biosorption for both metal ions. The pseudo-first order kinetic model was unable to describe the biosorption process throughout the effective biosorption period while the modified pseudo-first order kinetics gave a better fit but could not predict the experimentally observed equilibrium capacities. The pseudo-second order kinetics gave a better fit to the experimental data over the temperature range from 291 to 347 K and the equilibrium capacity increased from 15.73 to 19.22 mg g^?1 for copper(II) and from 23.74 to 26.27 for lead(II).Activation energy was higher for lead(II) (22.40 kJ mol^?1) than for copper(II) (20.36 kJ mol^?1). The free energy of activation was higher for lead(II) than for copper(II) and the values of ΔH* and ΔS* indicate that the contribution of reorientation to the activation stage is higher for lead(II) than copper(II). This implies that lead(II) biosorption is more spontaneous than copper(II) biosorption.Equilibrium studies showed that the Langmuir isotherm gave a better fit for the equilibrium data indicating monolayer coverage of the biosorbent surface. There was only a small interaction between metal ions when simultaneously biosorbed and cation competition was higher for the Cu-Pb system than for the Pb-Cu system. Desorption studies and the Dubinin–Radushkevich isotherm and energy parameter, E, also support the ion-exchange mechanism.     

Nitrification in a vertically moving biofilm system

A laboratory continuous feed biofilm reactor, comprising a bulk fluid reactor, a biofilm plastic module, a feed tank, and pneumatic devices and controls, was operated for a total period of 257 days, including seeding time, to treat domestic-strength synthetic wastewater under increasing ammonium nitrogen (NH(4)(+)--N) loading rates, ranging from 0.17+/-0.01 (0.71+/-0.06 gm(-2)d(-1)) to 0.70+/-0.02 kgm(-3)d(-1) (2.9+/-0.1 gm(-2)d(-1)). The biofilm plastic module was moved vertically in and out of the wastewater in continuous cycles. The maximum NH(4)(+)-N removal rate was reached during the maximum loading phase, when a NH(4)(+)--N loading rate of 0.70+/-0.02 kgm(-3)d(-1) (2.9+/-0.1 gm(-2)d(-1)) was applied to the system. During this loading period, the average NH(4)(+)--N removal rate was 0.30+/-0.10 kgm(-3)d(-1) (1.30+/-0.40 gm(-2)d(-1)).     

Application of a chemically modified green macro alga as a biosorbent for phenol removal

Phenol and substituted phenols are toxic organic pollutants present in tannery waste streams. Environmental legislation defines the maximum discharge limit to be 5–50 ppm of total phenols in sewers. Thus the efforts to develop new efficient methods to remove phenolic compounds from wastewater are of primary concern. The present work aims at the use of a modified green macro alga (Caulerpa scalpelliformis) as a biosorbent for the removal of phenolic compounds from the post-tanning sectional stream. The effects of initial phenol concentration, contact time, temperature and initial pH of the solution on the biosorption potential of macro algal biomass have been investigated. Biosorption of phenol by modified green macro algae is best described by the Langmuir adsorption isotherm model. Biosorption kinetics of phenol onto modified green macro algal biomass were best described by a pseudo second order model. The maximum uptake capacity was found to be 20 mg of phenol per gram of green macro algae. A Boyd plot confirmed the external mass transfer as the slowest step involved in the biosorption process. The average effective diffusion coefficient was found to be 1.44 × 10⁻⁹ cm²/s. Thermodynamic studies confirmed the biosorption process to be exothermic.     

Biological treatment of synthetic wastewater containing 2,4 dichlorophenol (DCP) in an activated sludge unit

Chlorophenol compounds present in many chemical industry wastewaters are resistant to biological degradation because of the toxic effects of such compounds on microorganisms. Synthetic wastewater containing different concentrations of 2,4 dichlorophenol (DCP) was subjected to biological treatment in an activated sludge unit. Effects of feed DCP concentration on COD, DCP, and toxicity removals and on sludge volume index were investigated at a constant sludge age of 10 days and hydraulic residence time (HRT) of 25 h. The Resazurin method based on dehydrogenase activity was used for assessment of toxicity for the feed and effluent wastewater. Percent COD, DCP, and toxicity removals decreased and the effluent COD, DCP, and toxicity levels increased with increasing feed DCP concentrations above 150 mgl(-1) because of inhibitory effects of DCP. Biomass concentration in the aeration tank decreased and the sludge volume index (SVI) increased with feed DCP concentrations above 150 mgl(-1) resulting in lower COD and DCP removal rates. The system should be operated at feed DCP concentrations of less than 150 mgl(-1) in order to obtain high COD, DCP, and toxicity removals.     

Removal of basic dye (Astrazon Blue FGRL) using macroalga Caulerpa lentillifera

The macroalga Caulerpa lentillifera was found to have adsorption capacity for a basic dye, Astrazon Blue FGRL. For the whole range of concentrations employed in this work (20-1280 mgl(-1)), the adsorption reached equilibrium within the first hour. The kinetic data corresponded well with the pseudo second-order kinetic model where the rate constants decreased as initial dye concentrations increased. At low dye concentrations (20-80 mgl(-1)), an increase in the adsorbent dosage resulted in a higher removal percentage of the dye, but a lower amount of dye adsorbed per unit mass (q). The adsorption isotherm followed both the Langmuir and Freundlich models within the temperature range employed in this work (18-70 degrees C). The highest maximum adsorption capacity (q(m)) was obtained at 50 degrees C. The enthalpy of adsorption was estimated at 14.87 kJmol(-1) suggesting a chemical adsorption mechanism.     

Phosphate uptake and release rates with different carbon sources in biological nutrient removal using a SBR

A three-step sequencing batch reactor (SBR) was used for nutrient removal from synthetic wastewater with different glucose-organic acid mixtures (1/1). Acetic, butyric, propionic and citric acids were used as organic acids along with glucose. The operation consisted of anaerobic, anoxic and oxic (An/Ax/Ox) phases with durations of 2/1/4.5h. Sludge age was kept constant for 10 days. Phosphate release and uptake rates were determined for different glucose-organic acid mixtures in the feed wastewater. Maximum phosphate uptake (8.1mgPl(-1)h(-1)) and release rates (2.23mgPl(-1)h(-1)) were obtained with the glucose-citric acid mixture. The highest (96%) percent phosphate removal at the end of the nutrient removal cycle (7.5h) was also obtained with the glucose-citric acid mixture while the glucose-acetic acid mixture resulted in comparable percent phosphate removal (95%).     

Para-chlorophenol containing synthetic wastewater treatment in an activated sludge unit: effects of hydraulic residence time

Due to the toxic nature of chlorophenol compounds present in some chemical industry effluents, biological treatment of such wastewaters is usually realized with low treatment efficiencies. Para-chlorophenol (4-chlorophenol, 4-CP) containing synthetic wastewater was treated in an activated sludge unit at different hydraulic residence times (HRT) varying between 5 and 30 h while the feed COD (2500 mg l(-1)), 4-CP (500 mg l(-1)) and sludge age (SRT, 10 days) were constant. Effects of HRT variations on COD, 4-CP, toxicity removals and on settling characteristics of the sludge were investigated. Percent COD removals increased and the effluent COD concentrations decreased when HRT increased from 5 to 15 h and remained almost constant for larger HRT levels. Nearly, 91% COD and 99% 4-CP removals were obtained at HRT levels above 15 h. Because of the highly concentrated microbial population at HRT levels of above 15 h, low effluent (reactor) 4-CP concentrations and almost complete toxicity removals were obtained. High biomass concentrations obtained at HRT levels above 15 h were due to low 4-CP contents in the aeration tank yielding negligible inhibition effects and low maintenance requirements. The sludge volume index (SVI) decreased with increasing HRT up to 15 h due to high biomass concentrations at high HRT levels resulting in well settling sludge with low SVI values. Hydraulic residence times above 15 h resulted in more than 90% COD and complete 4-CP and toxicity removals along with well settling sludge.     

Attenuation of divalent toxic metal ions using natural sericitic pyrophyllite

The present study investigated the effectiveness of an inexpensive and ecofriendly alumino silicate clay mineral, sericitic pyrophyllite, as an adsorbent for the possible application in the removal of some divalent toxic metal cations such as Pb(2+), Cu(2+)and Zn(2+) from aqueous systems. Batch scale equilibrium adsorption studies were carried out for a wide range of initial concentration from 24.1 to 2410mumolL(-1) for lead, 78.65 to 7865mumolL(-1) for copper and 76.45 to 7645mumolL(-1) for zinc solutions. The removal of Pb(2+) was almost complete at low concentration (maximum lead removal capacity, LRC, 32mg of lead/g of pyrophyllite) with 10gL(-1) of adsorbent in a 30min equilibration time. The effects of temperature on adsorption of heavy metal ions were studied. The applicability of the Langmuir, Freundlich and Dubinin-Radushkevich adsorption models in each case of lead, copper and zinc adsorption was examined separately at different temperatures. The adsorption process was found to be endothermic and the Freundlich adsorption model was found to represent the data at different temperatures more suitably.     

Trace element speciation in poultry litter

Trace elements are added to poultry feed for disease prevention and enhanced feed efficiency. High concentrations are found in poultry litter (PL), which raises concerns regarding trace element loading of soils. Trace metal cation solubility from PL may be enhanced by complexation with dissolved organic carbon (DOC). Mineralization of organo-As compounds may result in more toxic species such as As(III) and As(V). Speciation of these elements in PL leachates should assist in predicting their fate in soil. Elemental concentrations of 40 PL samples from the southeastern USA were determined. Water-soluble extractions (WSE) were fractionated into hydrophobic, anionic, and cationic species with solid-phase extraction columns. Arsenic speciation of seven As species, including the main As poultry feed additives, roxarsone (ROX; 3-nitro-4-hydroxyphenylarsonic acid) and p-arsanilic acid (p-ASA; 4-aminophenylarsonic acid), was performed by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS). Total As concentrations in the litter varied from 1 to 39 mg kg(-1), averaging 16 mg kg(-1). Mean total Cu, Ni, and Zn concentrations were 479, 11, and 373 mg kg(-1), respectively. Copper and Ni were relatively soluble (49 and 41% respectively) while only 6% of Zn was soluble. Arsenic was highly soluble with an average of 71% WSE. Roxarsone was the major As species in 50% of PL samples. However, the presence of As(V) as the major species in 50% of the PL samples indicates that mineralization of ROX had occurred. The high solubility of As from litter and its apparent ready mineralization to inorganic forms coupled with the large quantity of litter that is annually land-applied in the USA suggests a potential detrimental effect on soil and water quality in the long term.     

Transport of gellan gum microbeads through sand: an experimental evaluation for encapsulated cell bioaugmentation

Transport of 10-40 microm gellan gum microbeads was studied in horizontal sand columns to evaluate the feasibility of using gel-encapsulated bacteria for bioaugmentation of contaminated aquifers. Three 5.2 x 110 cm columns were packed with sand (column A: 0.5-2 mm, column B: 0.25-2 mm, and column C: 0.125-2 mm). Microbeads in artificial groundwater were injected at 0.5 l h(-1) during intermittent 12-h periods. Breakthrough of microbeads increased with injection time, varying as a descending function of travel distance. After 72 h of injection, about 75% of injected microbeads were dispersed across a 5-110 cm distance from the inlet in column A, compared to 78% across a 5-50 cm in column B, and 76% across a 5-20 cm in column C. The wider dispersion of microbeads across the length of column A, compared to those observed in columns B and C, suggests a higher potential for the formation of a uniform bioactive zone of encapsulated cells across a sandy aquifer with such grain size distribution and hydrodynamic properties.     

Bioproduction of ferric sulfate used during heavy metals removal from sewage sludge

Toxic metals removal from wastewater sewage sludge can be achieved through microbial processes involving Acidithiobacillus ferrooxidans. The oxidation of ferrous ions by A. ferrooxidans, cultured in sewage sludge filtrate, was studied in both batch and continuous flow stirred tank reactors. Sewage sludge filtrate containing natural nutrients (phosphorus and nitrogen) was recovered as effluent following the dehydration of a primary and secondary sludge mixture. Batch and continuous flow stirred tank reactor tests demonstrated that A. ferrooxidans were able to grow and completely oxidize ferrous iron in a culture medium containing more than 80% (v v(-1)) sewage sludge filtrate with 10 g Fe(II) L(-1) added. Toxic levels were reached when total organic carbon in the sewage sludge filtrate exceeded 250 mg L(-1). The ferric iron solution produced in the sludge filtrate by A. ferrooxidans was used to solubilize heavy metals in primary and secondary sludge. The solubilization of Cu, Cr, and Zn yielded 71, 49, and 80%, respectively. This is comparable with the yield percentages obtained using a FeCl(3) solution. The cost of treating wastewater sewage sludge by bioproducing a ferric ion solution from sewage sludge is three times less expensive than the conventional method requiring a commercial ferric chloride solution.     

Relative movement and soil fixation of soluble organic and inorganic phosphorus

There is considerable concern about pollution of surface waters with P. Although most of the research has focused on inorganic P in surface runoff, it has recently become possible to easily follow the fate of soluble organic P forms in soils and waters. Two experiments were performed to compare the relative mobility and soil fixation affinity of orthophosphate monoesters, orthophosphate diesters, and soluble inorganic P. We used three P substrates, 4-methylumbelliferyl phosphate (MUP), deoxyribonucleic acid (DNA), and KH(2)PO(4) in (i) a soil column experiment and (ii) a soil P adsorption test tube experiment. Shortly after columns were prepared, approximately two pore volumes of 0.005 M CaCl(2) were passed through 25 cm length columns containing 10 cm of loamy sand amended with approximately 10 mg P as MUP, DNA, or KH(2)PO(4) above 15 cm of nonamended loamy sand. The total net quantity of 757.8 microg P 2L(-1) of orthophosphate diesters in the leachate from the DNA columns exceeded the net quantity of orthophosphate monoesters in leachate from the MUP columns (4.6 microg P 2L(-1)) and soluble inorganic P from the KH(2)PO(4) columns (34.0 microg P 2L(-1)). Adsorption of soluble organic and inorganic P in the test tube experiment yielded similar results: DNA, containing orthophosphate diesters, had a relatively low affinity for soils. In both experiments, high concentrations of other P compounds were identified in samples treated with organic P substrates, suggesting enzymatic hydrolysis by native soil phosphatase enzymes. These findings indicate that repeated application of organic forms of P could lead to significant leaching of P to ground water.     

Transport of sulfadiazine in undisturbed soil columns: effects of flow rate, input concentration and pulse duration

Antibiotics reach soils via spreading of manure or sewage sludge. Knowledge on the transport behavior of antibiotics in soils is needed to assess their environmental fate. The effect of flow rate and applied mass, i.e., input concentration and pulse duration, on the transport of 14C-sulfadiazine (SDZ; 4-aminoN-pyrimidin-2-yl-benzenesulfonamide) was investigated with soil column experiments and numerical studies. Sulfadiazine was applied in pulses (6.8, 68 or 306 h) under steady-state (0.051 and 0.21 cm h(-1)) and intermittent flow conditions and at two input concentrations (0.57 and 5.7 mg L(-1)). Breakthrough curves (BTCs) of 14C were measured and for one experiment concentrations of SDZ, and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline (An-SDZ) and N(1)-2-(4-hydroxypyrimidinyl)benzenesulfanilamide (4-OH-SDZ) were determined. After finalizing the leaching experiments, 14C was quantified in different slices of the columns. A lower flow rate led to remarkably lower eluted masses compared with the higher flow rates. All BTCs could be described well using a three-site attachment-detachment model for which a common set of parameters was determined. However, the BTC obtained with the high input concentration was slightly better described with a two-site isotherm-based model. The prediction of the concentration profiles was good with both model concepts. The fitted sorption capacities decreased in the order SDZ > 4-OH-SDZ > An-SDZ. Overall, the experiments reveal the presence of similar mechanisms characterizing SDZ transport. The dependence of model performance on concentration implies that although the three-site attachment-detachment model is appropriate to predict the transport of SDZ in soil columns, not all relevant processes are adequately captured.