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.     

Phosphorus movement and speciation in a sandy soil profile after long-term animal manure applications

Long-term application of phosphorus (P) with animal manure in amounts exceeding removal with crops leads to buildup of P in soil and to increasing risk of P loss to surface water and eutrophication. In most manures, the majority of P is held within inorganic forms, but in soil leachates organic P forms often dominate. We investigated the mobility of both inorganic and organic P in profile samples from a noncalcareous sandy soil treated for 11 yr with excessive amounts of pig slurry, poultry manure, or poultry manure mixed with litter. Solution 31P nuclear magnetic resonance spectroscopy was used to characterize NaOH-EDTA-extractable forms of P, corresponding to 64 to 93% of the total P concentration in soil. Orthophosphate and orthophosphate monoesters were the main P forms detected in the NaOH-EDTA extracts. A strong accumulation of orthophosphate monoesters was found in the upper layers of the manure-treated soils. For orthophosphate, however, increased concentrations were found down to the 40- to 50-cm soil layers, indicating a strong downward movement of this P form. This was ascribed to the strong retention of orthophosphate monoesters by the solid phase of the soil, preventing orthophosphate sorption and facilitating downward movement of orthophosphate. Alternatively, mineralization of organic P in the upper layers of the manure-treated soils may have generated orthophosphate, which could have contributed to the downward movement of the latter. Leaching of inorganic P should thus be considered for the assessment and the future management of the long-term risk of P loss from soils receiving large amounts of manure.     

Fate of dimethyldiselenide in soil

Volatilization of dimethyldiselenide (DMDSe) is one of the most important processes for removing selenium (Se) from Se-contaminated environments. However, the fate of DMDSe in soil is not known. In this study, we monitored the changes of DMDSe in the head space of soil samples spiked with known amounts of DMDSe gas, and fractionated and speciated the resulting Se forms in soil. Dimethyldiselenide was highly dissolved in water in a closed air-water system and was highly sorbed onto soil in a closed air-soil system. Chemical and biological transformations of DMDSe in soil converted a large amount of DMDSe to nonvolatile Se compounds. Elemental Se [Se(0)] and nonvolatile organic Se were the major forms of Se transformed from spiked DMDSe. Microbial conversion of DMDSe to dimethylselenide (DMSe) in soil increased the production of DMSe. Calculation of the mass recovery showed that about 85 to 93% of the added DMDSe was recovered as Se(0), organic Se, organic material Se (OM-Se), Se(IV), and volatile organic Se in the head space in the non-autoclaved soils and 50 to 70% of the added DMDSe was recovered in the autoclaved soils. These results indicate that DMDSe is not a stable form of Se, and it may be one of the important precursors of DMSe in the soil environment.     

Associated release of magnesium and phosphorus from active and abandoned dairy soils

Dairy manure application to soils can result in phosphorus (P)-related degradation of water quality. The P in these manure-impacted soils can be labile even years after abandonment and under conditions normally associated with high P stability. Failure of P to stabilize with time compounds the environmental consequences of dairy manure disposal, especially on sandy soils. The objectives of this study were to compare chemical characteristics of active and abandoned dairy manure-impacted soils and minimally impacted soils and to assess the continuous release of P in relation to sparingly soluble salts using repeated water extractions, X-ray diffraction, and speciation modeling of column leachates. Soil samples from Ap horizons were collected from nine highly manure-impacted (total P > 1000 mg P kg(-1) soil) areas on four active and five abandoned dairies and four minimally impacted soils (total P < 200 mg P kg(-1) soil). Soil extracts were analyzed for electrical conductivity (EC), soluble reactive phosphorus (SRP), Ca, Mg, Na, and K. The EC of the soil solutions decreased as active dairy > abandoned dairy > minimally impacted soils. Release of Mg and SRP were significantly correlated (r2 = 0.68) and did not decline after abandonment; Ca release was not correlated with SRP (r2 = 0.01), and declined significantly (p < 0.05) after abandonment. Speciation data from column leachates suggested that Mg-P phases and/or the most soluble Ca-P phases could control P solution activities. An implication of this study is that P stabilization via crystallization of calcium phosphates (even at near-neutral pH) may be preempted by Mg-P association. Thus, mechanisms to minimize P release may require P-retaining soil amendments or management of animal rations to eliminate Mg-P formation.     

Influence of phytase addition to poultry diets on phosphorus forms and solubility in litters and amended soils

Diet modification to decrease phosphorus (P) concentration in animal feeds and manures can reduce surpluses of manure P in areas of intensive animal production. We generated turkey and broiler litters from two and three flock trials, respectively, using diets that ranged from "high" to "low" in non-phytate phosphorus (NPP) and some of which contained feed additives such as phytase. Phosphorus forms in selected litters were analyzed by sequential chemical fractionation and solution (31)P nuclear magnetic resonance (NMR) spectroscopy. Selected litters were also incubated with four contrasting soils. Reducing dietary NPP and using phytase decreased total P in litters by up to 38%. Water-soluble phosphorus (WSP) in litters was decreased 21 to 44% by feeding NPP closer to animal requirement, but was not affected by phytase addition. Solution (31)P NMR spectroscopy showed that feeding NPP closer to requirement decreased orthophosphate in litters by an average of 38% and that adding phytase to feed did not increase the concentration of orthophosphate in litters. Phytase also decreased phytate P in litters by 25 to 38%, demonstrating that it increases phytate P hydrolysis. Incorporation of litters with soils at the same total P rate increased WSP in soils relative to the control; this increase was correlated to soluble P added with litters at 5 d, but not by 29 d. Changes in soil Mehlich-3 phosphorus (M3-P) were related to total P added in litter, rather than soluble P. We conclude that feeding NPP closer to requirement and using feed additives such as phytase decrease total P concentrations in litters, while having little effect on P solubility in litters and amended soils.     

Plant-available and water-soluble phosphorus in soils amended with separated manure solids

Physical, chemical, or biological treatment of animal liquid manure generally produces a dry-matter rich fraction (DMF) that contains most of the initial phosphorus (P). Our objective was to assess the solubility and plant availability of P from various DMFs as a function of soil P status. Eight different DMFs were obtained from liquid swine (LSM) and dairy cattle (LDC) manures treated by natural decantation, anaerobic digestion, chemical flocculation, composting, or mechanical separation. The DMFs were compared with mineral P fertilizer in a pot experiment with oat ( L.) grown in four soils with varied P-fixing capacities and P saturation levels. The DMFs were added at a rate of 50 mg P kg soil and incubated 14 d before seeding. Soil water-extractable P (P) at all water:soil extraction ratios (2:1, 20:1, and 200:1) was slightly higher when DMFs were derived from LDC rather than LSM. Soil P at the 2:1 ratio was lower with anaerobically digested LSM. At the 2:1 extraction ratio, DMF P was less soluble than mineral P as P saturation in soils increased. In soils with a lower P-fixing capacity, DMF P appeared less water soluble than mineral P under 20:1 and 200:1 extraction ratios. After 72 d of plant growth, DMFs produced yields comparable to mineral P fertilizer. Although the plant availability of P from DMFs was comparable to mineral P fertilizer, P from DMFs could be less vulnerable to leaching or runoff losses in soils with a high P saturation level or low P-fixing capacity.     

An examination of spin-lattice relaxation times for analysis of soil and manure extracts by liquid state phosphorus-31 nuclear magnetic resonance spectroscopy

Phosphorous (P)-31 nuclear magnetic resonance (NMR) spectroscopy is used in the analysis of P forms in extracts of soils and manures for environmental and agronomic purposes. Quantitative spectra require knowledge about spin-lattice relaxation times (T1) to ensure adequate delays between pulses. This paper determined T1 values of P forms in reconstituted (0.2 g in 0.7 mL(-1)) samples of freeze-dried 0.25 M NaOH plus 50 mM EDTA extracts of eight diverse soils (Aquept, Dystrochrept x 2, Hapludand, Rendoll, Udand, Haplostoll, and Orthod), three different manures (dairy cattle, deer, and sheep), and one epiphyte moss. Total concentrations in the reconstituted samples ranged from 5 to 175 mg Fe mL(-1), 2 to 62 mg Mn mL(-1), and 72 to 837 mg P mL(-1). Values of T1 for orthophosphate monoesters, orthophosphate diesters, and pyrophosphate varied from 0.42 to 1.69 s in soils and from 0.89 to 2.59 s in manures and the epiphyte. In contrast, T(1) for orthophosphate varied from 0.78 to 1.94 s in soils and 1.45 to 5.82 s in manures and the epiphyte. For quantitative 31P NMR, delay times should be three to five times the T1 value, translating to delays of 3 to 5 s for soils and up to 25 s for manures. If the required delay is too long then strategies such as adding paramagnetics could shorten T1, provided this does not increase line-broadening too much. A regression relationship was obtained between orthophosphate T1 values and the ratio of P concentration to Fe and Mn concentration on a w/v basis (r2= 0.97, P < 0.001), and between the T1 for all other compound classes and the ratio of P to Fe and Mn (r2= 0.70, P < 0.01). By combining measurement of Fe, Mn, and P in the reconstituted extract and these relationships, T1 can be estimated and the appropriate delay time used. If T1 is not considered and the delay time is too short, some peaks will be under- or over-represented and the relative distribution of P forms not quantitative.     

Phosphorus in runoff assessed by anion exchange resin extraction and an algal assay

Eutrophication of surface waters can be accelerated by agricultural inputs of phosphorus (P), provided that P is in a form that can be utilized by aquatic algae. We studied anion exchange resin (AER) extraction and a dual culture algal assay (DCAA) for the determination of potentially algal-available P in water samples without sediment preconcentration. Our material consisted of agricultural and forest runoff and wastewaters. The results obtained by the two methods were essentially equal when the samples contained only small amounts of particulate phosphorus (PP) in relation to dissolved molybdate-reactive phosphorus (DRP). However, in turbid agricultural runoff, P extracted with AER averaged 72% (n = 17) of the P yield of the 3-wk DCAA (R2 = 0.94). When the runoff samples were diluted for the AER extraction in the same manner as for the DCAA, the AER-P yield increased to 85% (n = 5) of DCAA-P. The minimum detectable value was greater for the AER test (41 microg L(-1) AER-extractable P) than for the DCAA (7 microg L(-1) DCAA-P). At concentrations greater than about 50 microg L(-1) AER-P or DCAA-P, the accuracy of the methods was satisfactory, with the coefficient of variation in replicated analyses being less than 10% for the AER test and less than 20% for the DCAA. Other anions competing for the exchange sites of the AER decreased P recovery by 15 to 20% when their equivalent concentration exceeded about 4 mmol, L(-1), and this effect was relatively constant over a large concentration range. We consider that AER extraction is a suitable low-cost method to estimate the algal availability of P in runoff samples.     

Phosphate adsorption by ferrihydrite-amended soils

New technology and approaches for reducing P in runoff from high sediment yield areas are essential due to implementation of increasingly rigorous water quality standards. The objectives of this research were to characterize ferrihydrite (Fe(5)HO(8).4H(2)O) in terms of its ability to adsorb P from soil solutions and relate its P adsorptive capacity to several soil properties that influence P mobility. A naturally occurring ferrihydrite, collected as an Fe oxide sludge by-product from a water treatment facility, was equilibrated with soil samples at equivalent rates of 0, 0.34, 3.36, 16.80, and 33.60 Mg ha(-1) for a 60-d period. Individual 2-g subsamples of each soil were then equilibrated with 0, 5, 10, 20, and 40 mg kg(-1) P in 20 mL of 0.01 M CaCl(2) on a reciprocating shaker for 24 h. After 24 h, P in solution was measured by colorimetric methods, and designated as final P concentrations. The data indicated that the unamended soils with a pH of <6.0 adsorbed, in some cases, 50 times more P than soils with a pH of >7.0. The final P concentrations, averaged for all initial P concentrations and ferrihydrite rates, ranged from 0.09 to 4.63 mg kg(-1), and were most highly correlated with pH (r = 0.844; P < or = 0.01), oxalate-extractable Fe (r = -0.699; P < or = 0.10), and dithionite-extractable Fe (r = -0.639; P < or = 0.10) contents of the unamended soils. In terms of individual soils, correlation coefficients (r) for final P concentrations versus ferrihydrite amendment rates indicated a statistically significant (P < or = 0.001) negative relationship at all initial P concentrations for most A horizons. The r values for the high Fe oxide content B horizon soils did not show a statistically significant response to ferrihydrite additions. The results indicate that P adsorption, in soils amended with ferrihydrite, will be greatest under acid pH conditions below the ferrihydrite zero point of charge (pH 5.77), and low incipient Fe oxide contents.     

Phosphorus release from a manure-impacted spodosol: effects of a water treatment residual

Long-term depositions of animal manures affect P dynamics in soils and can pose environmental risks associated with P losses. Laboratory studies were done on P solubility characteristics in a manure-impacted Immokalee soil (sandy, siliceous, hyperthermic Arenic Alaquod) and the effectiveness of water treatment residual (WTR) in controlling P leaching. Soil samples with contrasting initial total P concentrations were prepared by mixing samples of a manure-impacted surface A horizon and a minimally P-impacted E horizon. Effects of mixing various ratios of A and E horizons, WTR rates (0, 25, 50, and 100 g kg(-1)), and depths of WTR incorporation (mixed throughout the soil column or partially incorporated) on P leaching were determined. Between 62 and 77% of total P was released from the soil mixes by successive water extractions, suggesting a considerable buffering capacity of this manure-impacted soil to resupply P into solution. Between 224 and 408 mg kg(-1) P were leached during the 36-wk leaching period in the absence of WTR. Mixing WTRs with soil reduced soluble P concentration in leachates by as much as 99.8% compared with samples without WTR. Thoroughly mixing WTR with the entire soil column (15 cm) was much more efficient than mixing WTR with only the top 7.5 cm of soil. Calcium- and Mg-P forms appear to control P release in soils without WTR, whereas sorption-desorption reactions probably determine P leaching in WTR-treated samples. Soil P distribution in various chemical forms was affected by WTR additions. Data suggest that WTR-immobilized P is stable in the long term.     

Soil and surface runoff phosphorus relationships for five typical USA midwest soils

Excessively high soil P can increase P loss with surface runoff. This study used indoor rainfall simulations to characterize soil and runoff P relationships for five Midwest soils (Argiudoll, Calciaquaoll, Hapludalf, and two Hapludolls). Topsoil (15-cm depth, 241-289 g clay kg(-1) and pH 6.0-8.0) was incubated with five NH4H2PO4 rates (0-600 mg P kg(-1)) for 30 d. Total soil P (TPS) and soil-test P (STP) measured with Bray-P1 (BP), Mehlich-3 (M3P), Olsen (OP), Fe-oxide-impregnated paper (FeP), and water (WP) tests were 370 to 1360, 3 to 530, 10 to 675, 4 to 640, 7 to 507, and 2 to 568 mg P kg(-1), respectively. Degree of soil P saturation (DPS) was estimated by indices based on P sorption index (PSI) and STP (DPSSTP) and P, Fe, and Al extracted by ammonium oxalate (DPSox) or Mehlich-3 (DPSM3). Soil was packed to 1.1 g cm(-3) bulk density in triplicate boxes set at 4% slope. Surface runoff was collected during 75 min of 6.5 cm h(-1) rain. Runoff bioavailable P (BAP) and dissolved reactive P (DRP) increased linearly with increased P rate, STP, DPSox, and DPSM3 but curvilinearly with DPSSTP. Correlations between DRP or BAP and soil tests or saturation indices across soils were greatest (r > or = 0.95) for FeP, OP, and WP and poorest for BP and TPS (r = 0.83-0.88). Excluding the calcareous soil (Calciaquoll) significantly improved correlations only for BP. Differences in relationships between runoff P and the soil tests were small or nonexistent among the noncalcareous soils. Routine soil P tests can estimate relationships between runoff P concentration and P application or soil P, although estimates would be improved by separate calibrations for calcareous and noncalcareous soils.     

Particulate phosphorus and sediment in surface runoff and drainflow from clayey soils

Recent work has shown that a significant portion of the total loss of phosphorus (P) from agricultural soils may occur via subsurface drainflow. The aim of this study was to compare the concentrations of different P forms in surface and subsurface runoff, and to assess the potential algal availability of particulate phosphorus (PP) in runoff waters. The material consisted of 91 water-sample pairs (surface runoff vs. subsurface drainage waters) from two artificially drained clayey soils (a Typic Cryaquept and an Aeric Cryaquept) and was analyzed for total suspended solids (TSS), total phosphorus (TP), dissolved molybdate-reactive phosphorus (DRP), and anion exchange resin-extractable phosphorus (AER-P). On the basis of these determinations, we calculated the concentrations of PP, desorbable particulate phosphorus (PPi), and particulate unavailable (nondesorbable) phosphorus (PUP). Some water samples and the soils were also analyzed for 137Cs activity and particle-size distribution. The major P fraction in the waters studied was PP and, on average, only 7% of it was desorbable by AER. However, a mean of 47% of potentially bioavailable P (AER-P) consisted of PPi. The suspended soil material carried by drainflow contained as much PPi (47-79 mg kg-1) as did the surface runoff sediment (45-82 mg kg-1). The runoff sediments were enriched in clay-sized particles and 137Cs by a factor of about two relative to the surface soils. Our results show that desorbable PP derived from topsoil may be as important a contributor to potentially algal-available P as DRP in both surface and subsurface runoff from clayey soils.     

Wet chemical and phosphorus-31 nuclear magnetic resonance analysis of phosphorus speciation in a sandy soil receiving long-term fertilizer or animal manure applications

In areas under intensive livestock farming and with high application rates of animal manure, inorganic and organic phosphorus (P) may be leached from soils. Since the contribution of these P compounds to P leaching may differ, it is important to determine the speciation of P in these soils. We determined the effect of various fertilization regimes on the P speciation in NaOH-Na2EDTA (ethylenediaminetetraacetic acid) and water extracts of acidic sandy soil samples from the top 5 cm of grassland with wet chemical analysis and 31P nuclear magnetic resonance (NMR) spectroscopy. These soils had been treated for a period of 11 years with no fertilizer (control), N (no P application), N-P-K, or different animal manures. Inorganic P was highly elevated in the NaOH-Na2EDTA extracts of the soils amended with N-P-K or animal manures, while organic P increased only in the soil treated with pig slurry. Water-extractable P showed a similar trend. As indicated by 31P NMR, orthophosphate monoesters were the main organic P compounds in all soils. Our results suggest that long-term applications of large amounts of P fertilizer and animal manures caused an accumulation of inorganic P, resulting in an increase of the potential risk related to mobilization of inorganic P in the top 5 cm of these soils.     

Estimating runoff phosphorus losses from calcareous soils in the Minnesota River basin

Bioavailable phosphorus (BAP) in stormwater runoff is a key issue for control of eutrophication in agriculturally impacted watersheds. Laboratory experiments were conducted in soil runoff boxes to determine BAP content in simulated storm runoff in 10 (mostly) calcareous soils from the Minnesota River basin in southern Minnesota. The soluble reactive phosphorus (SRP) portion of the runoff BAP was significantly correlated with soil Mehlich-III P, Olsen P, and water-extractable P (all r2 > 0.90 and p < 0.001). A linear relationship (r2 = 0.88, p < 0.001) also was obtained between SRP in runoff and the phosphorus saturation index based on sorptivity (PSIs) calculated with sorptivity as a measure of the inherent soil P sorption capacity. Runoff levels of BAP estimated with iron oxide-impregnated paper were predicted well by various soil test P methods and the PSI, of the soils, but correlation coefficients between these variables and runoff BAP were generally lower than those for runoff SRP. Using these relationships and critical BAP levels for stream eutrophication, we found corresponding critical levels of soil Mehlich-III P and Olsen P (which should not be exceeded) to be 65 to 85 and 40 to 55 mg kg(-1), respectively.     

Soil variables for predicting potential phosphorus release in Swedish noncalcareous soils

The accumulation of P in agricultural soils due to fertilization has increased the risk of P losses from agricultural fields to surface waters. In risk assessment systems for P losses, both P release from soil to solution and transport mechanisms need to be considered. In this study, the overall objective was to identify soil variables for prediction of potential P release from soil to solution. Soils from nine sites of the Swedish long-term fertility experiment were used, each with four soil P levels. Phosphorus extractable with CaCl2 was used as an estimate of potential P release from soil to solution. Ammonium lactate-extractable phosphorus (P-AL) or NaHCO3-extractable phosphorus (Olsen P) could not be used alone for prediction of potential P release since soils with high phosphorus sorption capacity (PSC) released less P than soils with low PSC at the same soil test phosphorus (STP) level. Degree of phosphorus saturation (DPS) was calculated as Olsen P or P-AL as a percentage of PSC derived from P sorption isotherms or from Fe and Al extractable in ammonium oxalate. The CaCl2-extractable total phosphorus (CaCl2-TP) was exponentially related to these DPS values (r2 > or = 0.79). The CaCl2-TP was also linearly related to ratios between Olsen P or P-AL and a single-point phosphorus sorption index (PSI; r2 > or = 0.86). These ratios, which are easily determined and gave good correlations with CaCl2-TP, seemed to be the most useful estimates of potential P release for risk assessment systems.     

Effect of mineral and manure phosphorus sources on runoff phosphorus

Concern over nonpoint-source phosphorus (P) losses from agricultural lands to surface waters has resulted in scrutiny of factors affecting P loss potential. A rainfall simulation study was conducted to quantify the effects of alternative P sources (dairy manure, poultry manure, swine slurry, and diammonium phosphate), application methods, and initial soil P concentrations on runoff P losses from three acidic soils (Buchanan-Hartleton, Hagerstown, and Lewbeach). Low P (12 to 26 mg kg(-1) Mehlich-3 P) and high P (396 to 415 mg kg(-1) Mehlich-3 P) members of each soil were amended with 100 kg total P ha(-1) from each of the four P sources either by surface application or mixing, and subjected to simulated rainfall (70 mm h(-1) to produce 30 min runoff). Phosphorus losses from fertilizer and manure applied to the soil surface differed significantly by source, with dissolved reactive phosphorus (DRP) accounting for 64% of total phosphorus (TP) (versus 9% for the unamended soils). For manure amended soils, these losses were linearly related to water-soluble P concentration of manure (r2 = 0.86 for DRP, r2 = 0.78 for TP). Mixing the P sources into the soil significantly decreased P losses relative to surface P application, such that DRP losses from amended, mixed soils were not significantly different from the unamended soil. Results of this study can be applied to site assessment indices to quantify the potential for P loss from recently manured soils.     

Phosphorus speciation in manure-amended alkaline soils

Two common manure storage practices are stockpiles and lagoons. The manure from stockpiles is applied to soils in solid form, while lagoon manure is applied as a liquid. Soil amendment with manure in any form introduces a significant amount of phosphorus (P) that exists in both organic and inorganic forms. However, little is known about P speciation in manure stored under different conditions, or the subsequent forms when applied to soils. We used solution (31)P nuclear magnetic resonance (NMR) spectroscopy and conventional P fractionation and speciation methods to investigate P forms in dairy manure and liquid lagoon manure, and to study how long-term amendment with these manures influenced surface and subsurface soil P speciation. Our results show that the P forms in solid and lagoon manure are similar. About 30% of the total P was organic, mostly as orthophosphate monoesters. On a dry weight basis, total P was much higher in the solid manure. In the manure-amended soils the total P concentrations of the surface soils were similar, regardless of manure type. Total P in the subsurface soil was greater in the lagoon-manure-amended soil than the solid-manure-amended subsurface soil. However, the fraction of organic P was greater in the subsurface of the solid-manure-amended soil. The NMR results indicate that the majority of organic P in the soils is phytic acid, which is enriched in the surface soils compared with the subsurface soils. These results provide insight into P speciation and dynamics in manure-amended soils that will further increase our understanding on how best to manage manure disposal on soils.     

Multivariate analysis of trace metal levels in tannery effluents in relation to soil and water: a case study from Peshawar, Pakistan

Tannery effluents and relevant ground water and soil samples collected from various tanning industries of Peshawar were analyzed for Na, Ca, K, Mg, Fe, Mn, Cr, Co, Cd, Ni, Pb and Zn by the AAS method. The metal concentration data for the three media are reported in terms of basic statistical parameters, metal-to-metal correlations and linear regression analyses. Metal distributions in the three media were quite divergent and showed non-normal distributions with high standard deviation and skewness parameters. Sodium exhibited the highest mean levels of 1,277mg/L, 881mg/L and 12,912mg/kg in the effluent, ground water and soil samples, respectively. Among other metals, Cr concentrations were 410mg/L, 0.145mg/L, 100mg/kg and Ca, 278mg/L, 64.8mg/L, and 2,285mg/kg in the effluent, ground water and soil samples, respectively. Some significant correlations were observed between effluent and soils in terms of Na, Cr, Ni, Co and Pb. The ground water-soil interrelationship suggested that Na levels in the soil and ground water were significantly correlated with each other (r=0.486, P<0.01). Similarly, Cr in the soil is strongly correlated with Ca in ground water (r=0.486, P<0.01). These results were duly supported by the linear regression analysis of data. The source identification studies conducted using Principal Component Analysis (PCA) and Cluster Analysis (CA) evidenced that ground water and soil were being contaminated by the toxic metals emanating from the tannery effluents.     

The availability of copper in soils historically amended with sewage sludge, manure, and compost

Metals in soils amended with sewage sludge are typically less available compared with those in soils spiked with soluble metal salts. However, it is unclear if this difference remains in the long term. A survey of copper (Cu) availability was made in soils amended with sewage sludge, manure, and compost, collectively named organic amendments. Paired sets of amended and control soils were collected from 22 field trials where the organic amendments had aged up to 112 yr. Amended soils had higher total Cu concentrations (range, 2-220 mg Cu kg; median, 15 mg Cu kg) and organic C (range, 1-16 g kg; median, 4 g kg) than control soils. All samples were freshly spiked with CuCl, and the toxicity of added Cu to barley was compared between amended and control soils. The toxicity of added Cu was significantly lower in amended soils than in control soil in 15 sets by, on average, a factor of 1.4, suggesting that aged amendments do not largely increase Cu binding sites. The fraction of added Cu that is isotopic exchangeable Cu (labile Cu) was compared between control soils freshly spiked with CuCl and amended soils with both soils at identical total Cu concentrations. Copper derived from amendments was significantly less labile (on average 5.9-fold) than freshly added Cu in 18 sets of soils. This study shows that Cu availability after long-term applications of organic amendments is lower than that of freshly added Cu salts, mainly because of its lower availability in the original matrix and ageing reactions than because of increased metal binding sites in soil.     

Concomitant rock phosphate dissolution and lead immobilization by phosphate solubilizing bacteria (Enterobacter sp.)

This paper examines the potential value of phosphate solubilizing bacteria (Enterobacter cloacae) in the dissolution of rock phosphate (RP) and subsequent immobilization of lead (Pb) in both bacterial growth medium and soils. Enterobacter sp. showed resistance to Pb and the bacterium solubilized 17.5% of RP in the growth medium. Enterobacter sp. did not enhance Pb immobilization in solution because of acidification of bacterial medium, thereby inhibiting the formation of P-induced Pb precipitation. However, in the case of soil, Enterobacter sp. increased Pb immobilization by 6.98, 25.6 and 32.0% with the RP level of 200, 800 and 1600 mg P/kg, respectively. The immobilization of Pb in Pb-spiked soils was attributed to pyromorphite formation as indicated by XRD analysis. Inoculation of phosphate solubilizing bacteria with RP in soil can be used as an alternative technique to soluble P compounds which can cause eutrophication of surface water.