Salicylate coordination in metal-protochelin complexes.

Molybdenum (Mo) is an essential trace element for bacteria that is utilized in myriad metalloenzymes that directly couple to the biogeochemical cycling of nitrogen, sulfur, and carbon. In particular, Mo is found in the most common nitrogenase enzyme, and the scarcity and low bioavailability of Mo in soil may be a critical factor that contributes to the limitation of nitrogen fixation in forests and agroenvironments. To overcome this scarcity, microbes produce exudates that specifically chelate scarce metals, promoting their solubilization and uptake. Here, we have determined the structure and stability constants of Mo bound by protochelin, a siderophore produced by bacteria under Mo-depleted conditions. Spectrophotometric titration spectra indicated a coordination shift from a catecholate to salicylate binding mode for MoVI-protochelin (Mo-Proto) complexes at pH < 5. pKa values obtained from analysis of titrations were 4.8 ± 0.3 for MoVIO2H3Proto- and 3.3 ± 0.1 for MoVIO2H4Proto. The occurrence of negatively charged Mo-Proto complexes at pH 6 was also confirmed by mass spectrometry. K-edge Extended X-ray absorption fine structure spectroscopy confirmed the change in Mo coordination at low pH, and structural fitting provides insights into the physical architecture of complexes at neutral and acidic pH. These findings suggest that Mo can be chelated by protochelin across a wide environmental pH range, with a coordination shift occurring at pH < 5. This chelation and associated coordination shift may impact biological availability and mineral surface retention of Mo under acidic conditions.

Long-term broiler litter amendments can alter the soil's capacity to sorb monensin.

Monensin is a common antiparasitic drug given to poultry that contaminates poultry manure and bedding material (broiler litter). As broiler litter is commonly applied to agricultural fields as fertilizer, monensin could be released beyond the farm if it is not retained or degraded in the soil. This study aimed to assess the impact of long-term surface application of broiler litter (i.e., 17 years) on the capacity of pasture soil to sorb monensin. The soils were exposed to a range of monensin concentrations (0.18 to 1.81 µmol L-1), solution pH (pH 4-9), and temperatures (15, 25, and 35 °C) and monensin was measured as loss from solution (i.e., sorption). Soils receiving long-term litter applications were hypothesized to retain more monensin than unamended soils because they have higher organic matter concentrations. However, soils from broiler litter-amended fields sorbed 46% less monensin than soils from unamended fields, likely because broiler litter also increased soil pH. The sorption of monensin to soil was strongly influenced by pH, with an order of magnitude greater sorption at pH 4 than at pH 9. Both soils had similar capacity to sorb monensin under similar solution pH, despite differences in organic carbon content (with the broiler litter-amended having 25% greater relative to the unamended soil). Temperature did not significantly impact monensin sorption for either soil. Our findings suggest increasing soil pH, for instance through liming, could enhance mobility of monensin.

Stacking Time and Aluminum Sulfate Effects on Polyether Ionophores in Broiler Litter.

The use of ionophores as antiparasitic drugs plays an important role in US poultry production, especially in the broiler () industry. However, administered ionophores can pass through the bird's digestive system and appear in broiler litter, which, when applied to agricultural fields, can present an environmental hazard. Stacking (storing or stockpiling) broiler litter for some time might decrease the litter ionophore concentrations before land application. Because ionophores undergo abiotic hydrolysis at low pH, decreasing litter pH with acidic aluminum sulfate (alum) might also decrease ionophore concentrations. We assessed the change in ionophore concentrations in broiler litter in response to the length of time broiler litter was stored (stacking time) and alum addition. We spiked broiler litter with monensin and salinomycin, placed alum-amended litter (∼pH 4-5) and unamended litter (∼pH 8-9) into 1.8-m bins, and repeatedly sampled each bin for 112 d. Our findings showed that stacking broiler litter alone did not have an impact on monensin concentration, but it did slowly reduce salinomycin concentration by 55%. Adding alum to broiler litter reduced monensin concentration by approximately 20% relative to unamended litter, but it did not change salinomycin concentration. These results call for continued search for alternative strategies that could potentially reduce the concentration of ionophores in broiler litter before their application to agricultural soils.

Alum and Rainfall Effects on Ionophores in Runoff from Surface-Applied Broiler Litter.

Polyether ionophores, monensin, and salinomycin are commonly used as antiparasitic drugs in broiler production and may be present in broiler litter (bird excreta plus bedding material). Long-term application of broiler litter to pastures may lead to ionophore contamination of surface waters. Because polyether ionophores break down at low pH, we hypothesized that decreasing litter pH with an acidic material such as aluminum sulfate (alum) would reduce ionophore losses to runoff (i.e., monensin and salinomycin concentrations, loads, or amounts lost). We quantified ionophore loss to runoff in response to (i) addition of alum to broiler litter and (ii) length of time between litter application and the first simulated rainfall event. The factorial experiment consisted of unamended (∼pH 9) vs. alum-amended litters (∼pH 6), each combined with simulated rainfall at 0, 2, or 4 wk after litter application. Runoff from alum-amended broiler litter had 33% lower monensin concentration ( < 0.01), 57% lower monensin load ( < 0.01), 48% lower salinomycin concentration ( < 0.01), and 66% lower salinomycin load ( < 0.01) than runoff from unamended broiler litter when averaged across all events of rainfall. Ionophore losses to runoff were also less when rainfall was delayed for 2 or 4 wk after litter application relative to applying rainfall immediately after litter application. While the weather is difficult to predict, our data suggest that ionophore losses in runoff can be reduced if broiler litter applications are made to maximize dry time after application.

Release of nitrogen and phosphorus from poultry litter amended with acidified biochar.

Application of poultry litter (PL) to soil may lead to nitrogen (N) losses through ammonia (NH(3)) volatilization and to potential contamination of surface runoff with PL-derived phosphorus (P). Amending litter with acidified biochar may minimize these problems by decreasing litter pH and by retaining litter-derived P, respectively. This study evaluated the effect of acidified biochars from pine chips (PC) and peanut hulls (PH) on NH(3) losses and inorganic N and P released from surface-applied or incorporated PL. Poultry litter with or without acidified biochars was surface-applied or incorporated into the soil and incubated for 21 d. Volatilized NH(3) was determined by trapping it in acid. Inorganic N and P were determined by leaching the soil with 0.01 M of CaCl(2) during the study and by extracting it with 1 M KCl after incubation. Acidified biochars reduced NH(3) losses by 58 to 63% with surface-applied PL, and by 56 to 60% with incorporated PL. Except for PH biochar, which caused a small increase in leached NH(4) (+)-N with incorporated PL, acidified biochars had no effect on leached or KCl-extractable inorganic N and P from surface-applied or incorporated PL. These results suggest that acidified biochars may decrease NH(3) losses from PL but may not reduce the potential for P loss in surface runoff from soils receiving PL.