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Many challenges remain before we can fully understand the multifaceted role that natural organic matter (NOM) plays in soil and aquatic systems. These challenges remain despite the considerable progress that has been made in understanding NOM’s properties and reactivity using the latest analytical techniques. For nearly 4 decades, the International Humic Substances Society (IHSS, which is a non-profit scientific society) has distributed standard substances that adhere to strict isolation protocols and reference materials that are collected in bulk and originate from clearly defined sites. These NOM standard and reference samples offer relatively uniform materials for designing experiments and developing new analytical methods. The protocols for isolating NOM, and humic and fulvic acid fractions of NOM utilize well-established preparative scale column chromatography and reverse osmosis methods. These standard and reference NOM samples are used by the international scientific community to study NOM across a range of disciplines from engineered to natural systems, thereby seeding the transfer of knowledge across research fields. Recently, powerful new analytical techniques used to characterize NOM have revealed complexities in its composition that transcend the “microbial” vs. “terrestrial” precursor paradigm. To continue to advance NOM research in the Anthropocene epoch, a workshop was convened to identify potential new sites for NOM samples that would encompass a range of sources and precursor materials and would be relevant for studying NOM’s role in mediating environmental and biogeochemical processes. We anticipate that expanding the portfolio of IHSS reference and standard NOM samples available to the research community will enable this diverse group of scientists and engineers to better understand the role that NOM plays globally under the influence of anthropogenic mediated changes.

Background. Oncogenic rearrangements of the neuregulin 1 gene (NRG1) consist of a 5' partner fused to a 3' NRG1 sequence that retains the EGF-like domain, and are found in 0.2% of solid tumors including lung, breast and gastrointestinal (GI) cancers. Carcinomas of GI origin, including pancreatic and cholangiocarcinoma, represent around 20% of solid tumors harboring NRG1 fusions and there is no approved therapy for this group of cancers. The chimeric NRG1 oncoproteins bind to HER3/ERBB3 leading to trans-activation of other ERBB family members and trigger a signaling cascade that culminates in oncogenesis. Although targeting HER3 represents a rational therapeutic strategy for cancers harboring NRG1 fusions, this has remained relatively unexplored for NRG1 fusion-positive GI malignancies. In this study we investigated the efficacy of the anti-HER3 monoclonal antibody seribantumab in preclinical models of NRG1-driven GI cancers. Methods. We developed models of isogenic pancreatic cancer cells with NRG1 fusions by lentiviral-mediated cDNA expression of ATP1B1-NRG1 and SLC3A2-NRG1 fusions in immortalized pancreatic ductal cells (H6c7). Seribantumab efficacy was evaluated in isogenic cell lines and in patient-derived xenograft (PDX) models of pancreatic adenocarcinoma (CTG-0943, APP-NRG1 fusion) and intrahepatic cholangiocarcinoma (CH-07-0068, RBPMS-NRG1 fusion). Western blotting analysis was used to evaluate protein phosphorylation. Expression of NRG1 fusions was confirmed by RT-PCR and NGS. Results. Expression of NRG1 fusions in H6c7 cells resulted in enhanced phosphorylation of HER3 and AKT and increased sensitivity to afatinib, as compared to empty vector control cells (H6c7-EV). Treatment of H6c7-SLC3A2-NRG1 cells with seribantumab resulted in a dose-dependent inhibition of HER3 and AKT phosphorylation. Seribantumab treatment of H6c7-ATP1B1-NRG1 and H6c7-SLC3A2-NRG1 cells resulted in dose-dependent inhibition of cell growth with IC50 values of 0.05 and 0.2 µM, respectively. In contrast, growth of H6c7-EV cells was much less sensitive to seribantumab (IC50 > 1µM). Tumor growth inhibition was observed after administration of seribantumab to PDX mouse models of pancreatic adenocarcinoma and intrahepatic cholangiocarcinoma. While seribantumab (5 mg and 10 mg per dose, BIW) was equally effective to the clinical equivalent dose of afatinib (5 mg/kg QD) in the cholangiocarcinoma PDX model, the two doses of seribantumab were more effective than afatinib in the pancreatic cancer PDX model, causing tumor shrinkage of up to 55% (23-77% range). There was no shrinkage of afatinib-treated pancreatic PDX tumors. Our results here suggest that seribantumab is effective at reducing tumor growth in preclinical models of gastrointestinal cancers with NRG1 fusions. These data support the use of seribantumab to treat GI and other cancers with NRG1 fusions in the ongoing phase 2 CRESTONE study (NCT#04383210). Citation Format: Igor Odintsov, Allan J. Lui, Paul R. Bloom, Morana Vojnic, Shawn Leland, Marc Ladanyi, Romel Somwar. Preclinical activity of seribantumab in gastrointestinal cancers with NRG1 fusions [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2021; 2021 Apr 10-15 and May 17-21. Philadelphia (PA): AACR; Cancer Res 2021;81(13_Suppl):Abstract nr 935.

To study the structure and function of soil organic matter, soil scientists have performed alkali extractions for soil humic acid (HA) and fulvic acid (FA) fractions for more than 200 years. Over the last few decades aquatic scientists have used similar fractions of dissolved organic matter, extracted by resin adsorption followed by alkali desorption. Critics have claimed that alkali-extractable fractions are laboratory artifacts, hence unsuitable for studying natural organic matter structure and function in field conditions. In response, this review first addresses specific conceptual concerns about humic fractions. Then we discuss several case studies in which HA and FA were extracted from soils, waters, and organic materials to address meaningful problems across diverse research settings. Specifically, one case study demonstrated the importance of humic substances for understanding transport and bioavailability of persistent organic pollutants. An understanding of metal binding sites in FA and HA proved essential to accurately model metal ion behavior in soil and water. In landscape-based studies, pesticides were preferentially bound to HA, reducing their mobility. Compost maturity and acceptability of other organic waste for land application were well evaluated by properties of HA extracted from these materials. A young humic fraction helped understand N cycling in paddy rice (Oryza sativa L.) soils, leading to improved rice management. The HA and FA fractions accurately represent natural organic matter across multiple environments, source materials, and research objectives. Studying them can help resolve important scientific and practical issues.

Chemical characteristics of dissolved organic matter (DOM) extracted from an ombrotrophic bog in northern Minnesota by two methods – XAD-8 and DEAE-cellulose – were compared using 13C NMR spectroscopy, excitation–emission matrix fluorescence spectroscopy (EEMS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). DOM extracted with XAD-8, a relatively hydrophobic sorbent, had a larger 13C NMR signal in the aromatic carbon region, but DOM extracted by DEAE-cellulose, a weak anion exchanger, had a larger signal in the carboxylic carbon region. DOM extracts prepared by the two methods were similar in their overall chemical characteristics that serve as proxies for organic matter sources. For example, only small differences were observed in the fluorescence index (FI) values of the extracts, and all values were within the range expected for terrestrially-derived DOM. EEMS spectra of both extracts had “humic-like” peak A areas smaller than that of standard reference Suwannee River fulvic acid. Of 2801 distinct chemical formulas assigned during FT-ICR MS analysis of the two extracts, 66% were present in both; 15% were unique to the XAD-8 extract, and 19% were unique to the DEAE-cellulose extract. Van Krevelen plots showed that the DEAE-cellulose extract had more tannin-like and condensed aromatic entities and formulas with higher O/C ratios, whereas the XAD-8 extract had more lignin-like material and formulas with higher H/C ratios. Overall, differences in chemical characteristics of the extracts reflect the mechanisms by which the extractants operate.

Lake Pepin, a natural impoundment on the Upper Mississippi River, has water quality problems of high sedimentation rates and elevated phosphorus (P) levels. The majority of sediments in Lake Pepin come from river banks consisting of fine tills in the Minnesota River Basin. Since 1850, inorganic P concentrations in lake sediments have continuously increased. This study explored whether the increase in inorganic P concentrations can be explained through selective transport of fine particles combined with in-stream P adsorption. The measurements included total P (TP) content, P adsorption/desorption isotherms, and the solution equilibrium P concentration at zero adsorption (EPC) for various bank materials. Results showed that till bank materials are inherently high in TP (>400 mg kg), have strong P binding ability, and have low EPC (

Addition of organic residues and their composts to enhance soil fertility results in organic N mineralization and transformations that may have profound effects on chemical processes. Our hypothesis is that carbonate precipitation and dissolution reactions are driven by proton consumption and release by organic N mineralization and nitrification. In the present study we evaluated the role of N-rich animal waste on carbonate dissolution/precipitation in a range of soil types. To discriminate the effects of organic C mineralization from nitrification we added a nitrification inhibitor, dicyandiamide (DCD), which slows NH 4 + oxidation without interfering with soil C respiration. Calcareous and non-calcareous soils were incubated with a pasteurized chicken manure (PCM) amendment with and without nitrification inhibitor DCD and control soil with and without DCD. Soil solution pH, extractable NH 4 + and NO 3 − , CO 2 emission and the concentrations of major cations in soil solution were determined. PCM application without DCD resulted in a pH increase in the first few days of the incubation followed by a pH decrease. DCD application effectively inhibited the nitrification process and the reduction in soil pH. The high correlation between nitrification and the reduction in pH indicated that the nitrification process was the main source of protons released, which led to carbonate dissolution and CO 2 emission from CaCO 3 . Application of DCD to PCM reduced CO 2 emission in PCM amended soils, especially in the earlier part of the incubation of calcareous soils. Furthermore, we found a linear 0.7:1 relation between the sum of cations (mostly Ca 2 + plus Mg 2 + ) released to solution due to proton production by organic N mineralization and nitrification that occurred in all soils with PCM applied, without DCD. Whereas, application of DCD to the PCM treatment inhibited nitrification and there was little or no proton production.

Root and microbial respiration is considered to be the main source of CO2 production in soil; however, calcite dissolution in calcareous soils may contribute to the emitted CO2. The major aim of this research was to quantify the contribution of CaCO3 dissolution to CO2 emission from a soil with and without the addition of an organic residue. Emissions of CO2 and its δ13C from incubated noncalcareous (Golan Heights [GH], −26.23‰) and calcareous (Bet She'an [BS], −11.47‰) soils with and without the addition of a pasteurized chicken manure (PCM, −23.2‰) were determined. During 56 d of incubation, 445 and 1804 mg kg−1 CO2–C emitted from BS and GH soils, and PCM application caused additional emission of 2430 and 1884 mg kg−1 CO2–C, respectively. The NO3−–N concentrations in the control BS and GH soils were 46 and 133 mg kg−1 and PCM application increased it to 508 and 577 mg kg−1, respectively. The emitted CO2–δ13C from BS and GH soils were −20.0 ± 0.2‰ and −27.2 ± 0.09‰ and application of PCM changed it to −20.6 ± 0.42‰ and −23.7 ± 0.16‰, respectively. Consequently, the contributions of the inorganic source to CO2–C emission from BS without and with PCM and from GH with PCM were 113.4, 417.5, and 176 mg kg−1 (26.5, 14.5, and 5% of the total), respectively. We suggest that oxidation of organic matter, mineralization of organic N, NH4 nitrification, oxidation of organic S, and production of organic acids caused chemical dissolution of calcite and CO2 emission. Ignoring this process will result in overestimation of the respired C.

Restoration of wetland hydrology can produce ecological benefits but may have unintended consequences. We examined effects of altered water level on release of dissolved reactive phosphorus (DRP) and greenhouse gases (GHG) in soil cores from a marsh being evaluated for restoration. We also measured field concentrations of DRP and other constituents in wetland porewater. Intact cores from a sampling location with higher Fe and lower calcium carbonate (CaCO(3)) contents released more DRP than another location, and displayed higher DRP under completely saturated compared to partly drained conditions. Porewater samples collected from the high-Fe location also contained higher DRP levels. Chemical data suggest that redox-driven reactions largely controlled DRP levels at the high-Fe site, while CaCO(3) adsorption was more important at the low-Fe site. Over the long term, water table elevation may attenuate P draining from the wetland due to decreased mineralization. However, such measures may increase P release in the short term. Raising the water level in soil cores resulted in decreased nitrous oxide (N(2)O) emissions, increased methane (CH(4)) emissions, and an overall increase in total global warming potential (GWP). The proportion of total GWP contributed by N(2)O decreased from 14% to < or = 1% as water level was raised, while the proportion contributed by CH(4) increased from 10 to 20% to 60 to 80%. Restoration of hydrology in the Rice Lake wetland has the potential to affect both local water quality and global air quality. These combined effects complicate the cost-to-benefit analysis of such wetland restoration efforts.

Distribution coefficients (K(OC)) for Hg2+ binding by IHSS Pahokee peat humic acid (PHA) and humic acids separated from O-horizons and peats in a northern temperate forest were determined using a competitive ligand-exchange method. All measurements were made at low ratios of added Hg2+ to reduced S. The commonly used chelating agents, EGTA and DTPA, were found to be ineffective competitive ligands; thus, we used DL-penicillamine, a synthetic amino acid with a thiol group. Calculated free [Hg2+] at equilibrium is very low, ranging from 10(-26.4) at pH 1.9 to 10(-36.9) at pH 5.8. Corresponding log Koc values ranged from 22.6 to 32.8. The slope of the plot of pH versus log K(OC) was 2.68, suggesting that two or more protons are released when each Hg2+ is bound. This is consistent with binding of Hg2+ to bidentate thiol sites with some participation of a third weak-acid group, presumably a thiol. The 1:2 stoichiometry is consistent with X-ray spectroscopy data for Hg2+ bound to HA and with other pH-dependency results showing release of two protons with the binding of each Hg2+. Our K(OC) values are much greater than indicated by the data from most previous studies.

Methylmercury cation (CH3Hg+) is known to have a strong affinity for organic matter in soil, sedimentary, and aquatic environments. The objective of this study is to determine the dominant ligands binding CH3Hg+ in humic acids by evaluating several CH3Hg+-ligand complexation models, using mercury LIII-edge extended X-ray absorption fine structure (EXAFS). The model CH3Hg+ binding ligands examined in this study include thiol (-SH), hydrogen polysulfide (-SSH or -SSSH), sulfide (-S-), disulfide (-SS-), carboxyl (-COOH), and amine (-NH2). Based on the atomic geometry around mercury in each model structure, we distinguished CH3Hg+-binding ligands in two different humic acids (soil and aquatic). We observed CH3Hg+ preferentially binds to thiol ligands. After saturating reactive thiol ligands, the majority of CH3Hg+ binds to carboxyl ligands rather than to amine or other reduced sulfur ligands than thiol. We found no evidence of significant CH3Hg+-sulfide/disulfide or CH3Hg+-hydrogen polysulfide complexes in any samples. When CH3Hg+ binds to a humic ligand, the C-Hg bond in CH3Hg+ remains intact. Some heavy atoms are proximately coordinated around the mercury atom in the sample containing the highest CH3Hg+ levels used in this study.

We combined synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy and binding affinity studies to determine the coordination, geometry, and strength of methyl mercury, CH3Hg (II), bonding in soil and stream organic matter. Samples of organic soil (OS), potentially soluble organic substances (PSOS) from the soil, and organic substances from a stream (SOS) draining the soil were taken along a short “hydrological transect.” We determined the sum of concentrations of highly reduced organic S groups (designated Org-SRED), such as thiol (RSH), disulfane (RSSH), sulfide (RSR), and disulfide (RSSR), using sulfur K-edge XANES. Org-SRED varied between 27% and 64% of total S in our samples. Hg LIII-edge EXAFS analysis were determined on samples added CH3Hg (II) to yield CH3Hg (II)/Org-SRED ratios in the range 0.01–1.62. At low ratios, Hg was associated to one C atom (the methyl group) at an average distance of 2.03 ± 0.02 A and to one S atom at an average distance of 2.34 ± 0.03 A, in the first coordination shell. At calculated CH3Hg(II)/Org-SRED ratios above 0.37 in OS, 0.32 in PSOS, and 0.24 in SOS, the organic S sites were saturated by CH3Hg+, and O (and/or N) atoms were found in the first coordination shell of Hg at an average distance of 2.09 ± 0.01 A. Based on the assumption that RSH (and possibly RSSH) groups take part in the complexation of CH3Hg+, whereas RSSR and RSR groups do not, approximately 17% of total organic S consisted of RSH (+ RSSH) functionalities in the organic soil. Corresponding figures for samples PSOS and SOS were 14% and 9%, respectively. Competitive complexation of CH3Hg+ by halide ions was used to determine the average binding strength of native concentrations of CH3Hg (II) in the OS sample. Using data for Org-SRED, calculated surface complexation constants were in the range from 1016.3 to 1016.7 for a model RSH site having an acidity constant of mercaptoacetic acid. These values compare favorably with identically defined stability constants (log K1) for the binding of methyl mercury to thiol groups in well-defined organic compounds.

Increased use of humic substances in agriculture has generated intense interest among producers, consumers, and regulators for an accurate and reliable method to quantify humic acid (HA) and fulvic acid (FA) in raw ores and products. Here we present a thoroughly validated method, the new standardized method for determination of HA and FA contents in raw humate ores and in solid and liquid products produced from them. The methods used for preparation of HA and FA were adapted according to the guidelines of the International Humic Substances Society involving alkaline extraction followed by acidification to separate HA from the fulvic fraction. This is followed by separation of FA from the fulvic fraction by adsorption on a nonionic macroporous acrylic ester resin at acid pH. It differs from previous methods in that it determines HA and FA concentrations gravimetrically on an ash-free basis. Critical steps in the method, e.g., initial test portion mass, test portion to extract volume ratio, extraction time, and acidification of alkaline extract, were optimized for maximum and consistent recovery of HA and FA. The method detection limits for HA and FA were 4.62 and 4.8 mg/L, respectively. The method quantitation limits for HA and FA were 14.7 and 15.3 mg/L, respectively.

Chelator-buffering methods with N-(2-hydroxyethyl)ethylenedinitrilotriacetic acid (HEDTA) are used to elucidate Poaceae growth response to micronutrient metal activities including (Zn 2+ ), but reliable hydroponic methods that maintain stable (Zn 2+ ) for evaluating Zn deficiency in rice (Oryza sativa L.) have not been reported. The objective was to develop a chelator-buffered method that gauges rice growth response to (Zn 2+ ) in an otherwise chemically stable environment. Using GEOCHEM-PC to estimate solution activities, an aerobic HEDTA-nitrilotriacetic acid (NTA) dual-chelator method was developed that imposed five (Zn 2+ ) levels on cv. IR-36 seedlings for 21 d after transplanting (DAT) in a growth chamber. Control of pH 5.50 ± 0.05 using 3.0 mM2-(4-morpholino)-ethanesulfonic acid (MES) combined with periodic adjustment was critical to preserving target (Zn 2+ ). Solution treatments ranged from Zn deficient, where (Zn 2+ ) = 10 -10.0 M (0.25 μM total chelated Zn), to fully Zn sufficient where (Zn 2+ ) = 10 -8.8 M (4.00 μM total chelated Zn). Using 200.0 μM total chelated Fe(III), adequate Fe was maintained at (Fe 3+ ) = 10 -14.3 M. Phosphorous supply was controlled to prevent toxic P accumulation at low (Zn 2+ ). With increasing (Zn 2+ ), total biomass at 21 d ranged from 0.94 to 1.90 g plant -1 . Shoot Zn responded to (Zn 2+ ), not total chelated Zn 2+ , and roots responded similarly. Critical (Zn 2+ ) for normal growth was 10 -9.1 M, and leaf Zn-deficiency symptoms were observed at (Zn 2+ ) ≤10 -9.4 M (≤28 mg Zn kg -1 shoot). The HEDTA-NTA method provides a rapid and reliable means for evaluating Zn deficiency tolerance in IR-36 via diagnostic visual and physical symptoms in response to a range of (Zn 2+ ) levels.

The binding of Hg{sup 2+} in organic matter of soils and waters controls the transport and transformations of Hg in terrestrial and aquatic ecosystems. The authors developed a competitive complexation method using the strong complexation of Hg{sup 2+} by Br{sup {minus}} for determining the Hg{sup 2+} binding strength in organic soils at native and elevated Hg concentrations. The distribution coefficients determined in KBr suspensions for sorption of native HG{sup 2+} to soil organic carbon (SOC) (K{sub soc}) are in the range of 10{sup 22} to 10{sup 23}. The K{sub soc} significantly decreased with increased additions of Hg{sup 2+} and with decreasing pH. Using data for reduced organic S concentrations determined by x-ray absorption near-edge structure spectroscopy (XANES), the authors calculated surface complex formation constants on the order of 10{sup 32} for a model site having acidity constants of mercaptoacetic acid. This value is in fair agreement with the tabulated value of 10{sup 345} for Hg{sup 2+} binding in mercaptoacetic acid. At native Hg concentrations, formation constants and K{sub soc} values were similar for different types of soil organic matter along transects from uplands into wetlands, despite varying concentration of Hg and reduced organic S. Their adsorption data are consistent withmore » the conclusions from their previous extended x-ray absorption fine structure spectroscopy (EXAFS) study that in a humic acid and soil, Hg{sup 2+} ions bond in two-fold coordination involving one reduced S and one O or N.« less

Hornblende minerals are important in proton neutralization and base cation release processes in many soils. This study was conducted to determine the pH dependence of hornblende dissolution rates and the rate of proton consumption during weathering under laboratory conditions. Hornblende was crushed mechanically and purified by magnetic and density separation. The samples were initially weathered (22 days) in pH 4.0, 0.01mol/L HOAc-LiOAc buffer to minimize the effect of grinding on dissolution rates. The pH range investigated was from 3.4 to 4.6 at approximately 0.2 pH unit intervals. The hornblende dissolution experiment was conducted in a 0.01 mol/L HOAc-LiOAc buffer in batch-type reactors for 30 days. The rate of proton consumption was determined for both the initially weathered samples and for samples not initially weathered in 0.01 mol/L LiCl at pH near 4.0. The dissolution was nonstoichiometric during the study period, with preferential release of Al, Fe, and Mg relative to Si. Nearly linear kinetics were observed for the release of Si, but the release rates of Al, Fe, and Mg decreased with time. Hornblende dissolution rates in the pH range studied decreased as pH increased. The overall apparent linear reaction orders, with respect to solution pH, were found to be 0.71, 0.39, 0.42, and 0.79 for Al, Fe, Mg, and Si release, respectively. The reaction orders at pH values between 3.4 and 4.2 were lower than those between pH 4.2 and 4.6. The quantity of proton consumed was equivalent to the total charges of the cations released. The proton consumption rate of samples not initially weathered was five times higher than that of the initially weathered samples. Dissolution rates obtained in acetate buffer were 3 to 4 times higher than those obtained in unbuffered LiCl solution at comparable pH and ionic strengths. The rate of hornblende dissolution is a function of solution pH and concentration of organic ligand.

The dissolution rates of most primary and secondary minerals are promoted by the presence of proton- and complex-forming ligands. Effects on the rates of dissolution of hornblende by naturally occurring organic acids at concentrations commonly encountered in soil solutions s and surface waters was studied in a pH 4.0, 0.0 1M HOAc-LiOA c buffer. Crushed hornblende samples were purified by magnetic and density separation, followed by an initial period of weathering in a buffered aqueous solution for 39 d. After the initial weathering the rate of dissolution was measured at different concentrations of citric, oxalic, polygalacturonic, tannic, and fulvic acids at pH 4.0 for another 32 d in a batch-type reactor. Although nearly linear kinetics were observed for the release of Si, the release of At, Fe, and Mg decreased with time. The dissolution was nonstoichiometric during the study period with preferential release of At, Fe, and Mg relative to Si. All ligands studied were found to accelerate the dissolution process and the rates increased with solution concentrations of organic acids. The reaction orders with respect to dissolved organic C were generally low, ranging from near zero to 0.37 for different organic acids. At a concentration of 2.5 mM of dissolved C the relative effectiveness of these ligands on promoting dissolution was oxalic > citric > tannic > polygalacturonic > fulvic acid. The strengths of organic acids to promote dissolution is related to the quantity of phenolic and carboxylic functional groups present on the organic compounds, and it is related to the strength of the metal-ligand complex formed in solution or on the mineral surface.

Analysis of Hg(II) complexed by a soil humic acid (HA) using synchrotron-based X-ray absorption spectroscopy (XAS) revealed the importance of reduces sulfur functional groups (thiol (R-SH) and disulfide (R-SS-R)/disulfane (R-SSH)) in humic substances in the complexation of Hg(II). A two-coordinate binding environment with one oxygen atom and one sulfur atom at distances of 2.02 and 2.38 {angstrom}, respectively, was found in the first coordination shell of Hg(II) complexed by humic acid. Model calculations show that a second coordination sphere could contain one carbon atom and a second sulfur atom at 2.78 and 2.93 {angstrom}, respectively. This suggests that in addition to thiol S, disulfide/disulfane S may be involved with the complexation of Hg(II) in soil organic matter. The appearance of carbon atom in the second coordination shell suggests that one O-containing ligand such as carboxyl and phenol ligands rather than H{sub 2}O molecule is bound to the Hg(II). The involvement of oxygen ligand in addition to the reduced S ligands in the complexation of Hg(II) is due to the low density of reduced S ligands in humic substances. The XAS results from this experiment provided direct molecular level evidence for the preference of reduced S functional groups over oxygen ligandsmore » by Hg(II) in the complexation with humic substances.« less

Sulfur K-edge x-ray absorption near-edge structure spectroscopy (XANES) was used to identify multiple organic S oxidation states in aquatic and soil humic substances. The XANES results suggest that S in humic substances exists in four major oxidation groups similar to sulfate ester, sulfonate, sulfoxide, and thiol-sulfide. Thiol S cannot be separated from sulfide X and must be considered as a single thiol-sulfide peak. The second derivative spectra suggest the existence of thiophene and sulfone S. The relative quantities of each major S form in humic samples were estimated based on the integrated cross section of each s {r_arrow} p transition peak corresponding to different S oxidation states in the S K-edge XANES spectra. The XANES results of the four humic samples used in this study appear to reflect the environmental settings where the humic substances originally formed. The percentage of the most reduced organic S (thiol-sulfide and possibly thiophene) in humic substances follows the sequence:aquatic samples > organic soil sample > mineral soil sample. The percentage of most oxidized S (sulfate group) was the greatest in the humic substance from a mineral soil and the lowest in the aquatic humic substances.

The need to understand the biological reactivity of polymers has increased in response to the integration of biological waste treatment systems (e.g., composting and soil application) into waste management plans of communities worldwide. The purpose of this study was to evaluate the compostibility and fate of a commonly used, synthetic polymer that is present in most solid waste streams. This was accomplished using a laboratory-scale composting system, simulated solid waste, and crosslinked 14 C-polyacrylate. Commercial preparations were composed primarily of a high-molecular-weight fraction (>500 kDa) that was resistant to degradation. Only the unpolymerized monomers and low-molecular-weight oligomers (totaling about 8% of the commercial preparation) were readily degraded during composting. Polymer crosslinkages were also degraded rapidly. Degradation of the low-molecular-weight fractions was considered significant, because these fractions have demonstrated a greater mobility potential in soils. Molecular size distribution and infrared (IR) spectra of extractable organic fractions confirmed that the structural integrity of the polymer chains was maintained during composting. These residual, high-molecular-weight polyacrylates could improve soil structure, and should continue to degrade slowly leaving no toxic residues.

Boron is an essential plant nutrient having a narrow range between concentrations that cause deficiency or toxicity symptoms in plants. Boric acid (B[OH] 3 ) and silicic acid (Si[OH] 4 ) have many chemical similarities and both are thought to be associated with organic matter in soils. The objectives of this study were to investigate the variation in boric and silicic acid adsorption and desorption in low ash humic acid over a range of B and Si concentrations and pH values. Borate adsorption by humic acid increased significantly from pH 3.67 to 8.70. The data fit the Freundlich equation better than the Langmuir model at high pH ; however, both fit well at pH 10. The constant capacitance model predicted B adsorption and the pH maximum using catechol as the adsorbing ligand and published stability constants. The predicted adsorption envelope was narrower than experimental data. This could be due to variation in stability constants that result from variation in substitution on other sites on the aromatic ring. Inclusion of glucose and salicylate in the adsorption model would also broaden the adsorption envelope by increasing adsorption at pH > 9 and < 9, respectively. Desorption of B from humic acid appears to show hysteresis effects at pH 7.6 but not at pH 8.15 and 8.7. Generally, B will be easily released from HA as solution concentrations decrease. Silicic acid did not adsorb in humic acid. The stability constant of Si-catechol humate complexes is apparently too low for adsorption of Si to occur at the pH and solution concentrations used in this experiment.

Progress in determining nutrient availability in the rhizosphere is restricted by a lack of reliable and convenient methods for rhizosphere soil-water collection. A modified centrifugation method with a fluorocarbon (Fluorinert™,FC-70) as an immiscible displacement liquid was developed. Our objectives were to: i) obtain an adequate soil-water volume from a small rhizosphere sample within a reasonable time; ii) collect rhizosphere soil-water at container capacity (≈ 90% of field capacity) to determine soluble soil ions; and iii) evaluate FC-70 as an extractant. The soil used was a Beadle clay loam (fine, montmorillonitic mesic Typic Argiustoll) with low and high levels of CaCO3 (5 and 204g kg-1). Soil samples from the rhizosphere of 30-days-old sordan (sorghum (Sorghum bicolor L.), sudangrass (Sorghum sudanese L.) hybrid seedlings were thin-sectioned at 1-, 2- and 3-mm from the root surface. The extraction parameters (sample size, volume of extractant, relative centrifugal force and centrifugation time) were varied to determine optimal values. We obtained adequate amounts of aqueous solutions from moist soil (≈ 6 g) when mixed with 2 mL of FC-70, packed into a filter unit, and centrifuged for 1 hour at 14,500 × g. The displaced soil-water was analyzed by inductively coupled plasma spectrometry. The modified centrifugation technique with FC-70 offers a reliable, rapid, safe, and contamination-free method for obtaining unaltered soil-water from the rhizosphere, at a moisture content normally found in soil.

Summary The mineralogies of ‘Tirs’ (Typic Pelloxererts), and ‘Debs’ (Typic Haploxerolls and Typic Xerochrepts) soils of the Gharb plain in north-western Morocco are investigated, with special attention given to the determination of the nature of the smectitic phase using the lithium test (Li test) and the alkylammonium method. The sand and silt mineralogy of Tirs soils is dominated by quartz with small amounts of feldspars and kaolinite. The sand and silt fractions of Dehs soils also contain significant amounts of mica, chlorite, and interstratified phyllosilicates. The clay minerals of Tirs soils are predominantly a high-charge smectite. The estimated interlayer charge for this phase is 0.61 mol(c)/O10(OH)2 and the fraction of tetrahedral charge varies from 38 to 44%. Although the percentage tetrahedral charge is less than 50%, the smectitic phase behaves as beidellite with the Li test. Dehs clays are more heterogeneous, consisting of smectite, vermiculite, illite, kaolinite, chlorite, and interstratified illite/smectite and illite/vermiculite. The Li test and the alkylammonium method demonstrate that a high-charge smectite or vermiculite is interstratified with illite. A low-charge montmorillonite is also present both in Tirs and in Dehs soils. The high-charge beidellitic phase is believed to be a transformation product of mica, whilst the low charge montmorillonite is thought to be inherited from the parent material.

The rates and stoichiometry of hornblende dissolution were studied in batch reactors in 0.01 M HOAc-LiOAc buffers at pH 3.6–4.0 and 25 °C for three consecutive weathering cycles of 36, 45, and 34 days (total 115 days). The dissolution rates were obtained for two particle size fractions (0.11–0.25 and 0.25–0.50 mm in diameter) with initial surface areas of 0.098 and 0.086 m 2 g −1 , respectively. Results showed that dissolution rates were nonlinear and nonstoichiometric in the early stage of reaction. The rates were greatest in the first cycle, decreased with time, and became more linear and more stoichiometric as the experiment proceeded into the second and third cycles. A very rapid release of Ca during the initial stages of the reaction was due to 0.91% CaCO 3 impurity in the hornblende. Incongruence was greatest in the first cycle (0–36 days) with preferential release of Al, Fe, and Mg relative to Si and greater at higher pH. Stoichiometric dissolution was approached more rapidly at lower pH, suggesting that the extent of reaction is an important factor in attaining stoichiometric dissolution. By the third cycle (82–155 days), at pH 3.6, the reaction appeared to be stoichiometric. Nonstoichiometry resulted in the depletion Al, Mg, and Al, relative to Si with calculated mean depths of depletion of 7, 38, and 67 nm, respectively, at pH 4.0. Most of the depletion occurred during the first cycle (0–36 days). The pH dependence increased after the first cycle and order dependence of release of Si, Mg, and Al with respect to (H + ) during the second and third cycles was not significantly different from the previously reported value of 0.7. For Fe, however, the order dependence was only 0.36, reflecting the lack of stoichiometry at the higher pH values. Comparison of our second cycle data with data for samples that were dried after an initial weathering treatment showed that drying produced higher dissolution rates and more incongruence. The drying effect was greatest for Fe, with an increase in rate by a factor of 5.6 and least for Si with an increase by a factor of 2.1. Air drying appears to cause the surface of the hornblende to revert to a condition similar to unreacted samples. Comparison of data for dissolution in 0.01 M acetate with data obtained in 0.01 M LiCl suggests acetate increases the rate by about a factor of 3–4. The rate at pH 4.0 for total base release was significantly lower than previous results for experiments conducted for

Scanning electron microscopy was used to assess the weathering status of plagioclase and alkali feldspar grains isolated from sandy outwash soils located under three vegetation communities: mixed red and white pine, maple-basswood, and white cedar. Feldspars were selected for this study because they were the most common weatherable minerals in these sandy soils. A morphological weathering index, based on the percent of the surface of the feldspar grains covered with etch pits, was used to evaluate weathering intensity. Results revealed that significant pedogenic weathering has occurred in the surface and subsurface horizons of these soils compared to the parent material. Plagioclases were found to be much more weathered than alkali feldspars. Within the plagioclase solid solution series, the weathering index increased linearly with increasing Ca content as determined by energy dispersive X-ray analysis. Comparisons among the three sites showed that weathering environments under the pine and maple-basswood communities were relatively similar, being only slightly more intense under pine. The most intense weathering occurred under the white cedar community, particularly in the E horizon. Linear regression analyses showed that the weathering index for alkali feldspars was significantly related to soil pH (r2 = 0.30, p < 0.001). In the case of plagioclases, multiple linear regression analyses showed that the weathering index was significantly dependent on both Ca(Ca + Na) molar ratio and pH (r2 = 0.83, p < 0.001) , with 64% weight effect due to Ca(Ca + Na) ratio, and 19% due to pH.

A commonly cited constraint to growth of the humic products industry has been the lack of a widely accepted procedure for determining humic and fulvic acid contents of commercial products. Several procedures have been used, but none is considered sufficiently quantitative, reproducible, and capable of discerning adulterants in the products.

▪ Pollution control workers have proposed composting as a bioremediation method for the cleanup of contaminated soil and for the detoxification of hazardous organic chemicals. However, decomposition (mineralization to CO2 and H2O) may not always be enhanced by composting, and transformation products of unknown risk may accumulate during composting. This paper presents a scientifically based scheme to determine the ultimate fate of synthetic materials in a composting environment, and for studying factors that may control the degradation of specific chemicals including herbicides (e.g., substrate bioavailability, enzyme concentrations, environmental conditions).

Beneficial use of reclaimed wastewater (RW) and biosolids (BS) in soils is accompanied by large input of sewage-originated P. Prolonged application may result in P accumulation up to levelsBeneficial use of reclaimed wastewater (RW) and biosolids (BS) in soils is accompanied by large input of sewage-originated P. Prolonged application may result in P accumulation up to levels that impair plant nutrition, increase P loss, and promote eutrophication in downstream waters. This study aims to shed light on the RW- and BS-P forms in soils and to follow the processes that determine P reactivity, solubility, availability, and loss in RW and BS treated soils. The Technion group used sequential P extraction combined with measuring stable oxygen isotopic composition in phosphate (δ18OP) and with 31P-NMR studies to probe P speciation and transformations in soils irrigated with RW or fresh water (FW). The application of the δ18OP method to probe inorganic P (Pi) speciation and transformations in soils was developed through collaboration between the Technion and the UCSC groups. The method was used to trace Pi in water-, NaHCO3-, NaOH-, and HCl- P fractions in a calcareous clay soil (Acre, Israel) irrigated with RW or FW. The δ18OP signature changes during a month of incubation indicated biogeochemical processes. The water soluble Pi (WSPi) was affected by enzymatic activity yielding isotopic equilibrium with the water molecules in the soil solution. Further it interacted rapidly with the NaHCO3-Pi. The more stable Pi pools also exhibited isotopic alterations in the first two weeks after P application, likely related to microbial activity. Isotopic depletion which could result from organic P (PO) mineralization was followed by enrichment which may result from biologic discrimination in the uptake. Similar transformations were observed in both soils although transformations related to biological activity were more pronounced in the soil treated with RW. Specific P compounds were identified by the Technion group, using solution-state 31P-NMR in wastewater and in soil P extracts from Acre soils irrigated by RW and FW. Few identified PO compounds (e.g., D-glucose-6-phosphate) indicated coupled transformations of P and C in the wastewater. The RW soil retained higher P content, mainly in the labile fractions, but lower labile PO, than the FW soil; this and the fact that P species in the various soil extracts of the RW soil appear independent of P species in the RW are attributed to enhanced biological activity and P recycling in the RW soil. Consistent with that, both soils retained very similar P species in the soil pools. The HUJ group tested P stabilization to maximize the environmental safe application rates and the agronomic beneficial use of BS. Sequential P extraction indicated that the most reactive BS-P forms: WSP, membrane-P, and NaHCO3-P, were effectively stabilized by ferrous sulfate (FeSul), calcium oxide (CaO), or aluminum sulfate (alum). After applying the stabilized BS, or fresh BS (FBS), FBS compost (BSC), or P fertilizer (KH2PO4) to an alluvial soil, P availability was probed during 100 days of incubation. A plant-based bioassay indicated that P availability followed the order KH2PO4 >> alum-BS > BSC ≥ FBS > CaO-BS >> FeSul-BS. The WSPi concentration in soil increased following FBS or BSC application, and P mineralization further increased it during incubation. In contrast, the chemically stabilized BS reduced WSPi concentrations relative to the untreated soil. It was concluded that the chemically stabilized BS effectively controlled WSPi in the soil while still supplying P to support plant growth. Using the sequential extraction procedure the persistence of P availability in BS treated soils was shown to be of a long-term nature. 15 years after the last BS application to MN soils that were annually amended for 20 years by heavy rates of BS, about 25% of the added BS-P was found in the labile fractions. The UMN group further probed soil-P speciation in these soils by bulk and micro X-ray absorption near edge structure (XANES). This newly developed method was shown to be a powerful tool for P speciation in soils. In a control soil (no BS added), 54% of the total P was PO and it was mostly identified as phytic acid; 15% was identified as brushite and 26% as strengite. A corn crop BS amended soil included mostly P-Fe-peat complex, variscite and Al-P-peat complex but no Ca-P while in a BS-grass soil octacalcium phosphate was identified and o-phosphorylethanolamine or phytic acid was shown to dominate the PO fraction that impair plant nutrition, increase P loss, and promote eutrophication in downstream waters. This study aims to shed light on the RW- and BS-P forms in soils and to follow the processes that determine P reactivity, solubility, availability, and loss in RW and BS treated soils. The Technion group used sequential P extraction combined with measuring stable oxygen isotopic composition in phosphate (δ18OP) and with 31P-NMR studies to probe P speciation and transformations in soils irrigated with RW or fresh water (FW). The application of the δ18OP method to probe inorganic P (Pi) speciation and transformations in soils was developed through collaboration between the Technion and the UCSC groups. The method was used to trace Pi in water-, NaHCO3-, NaOH-, and HCl- P fractions in a calcareous clay soil (Acre, Israel) irrigated with RW or FW. The δ18OP signature changes during a month of incubation indicated biogeochemical processes. The water soluble Pi (WSPi) was affected by enzymatic activity yielding isotopic equilibrium with the water molecules in the soil solution. Further it interacted rapidly with the NaHCO3-Pi. The more stable Pi pools also exhibited isotopic alterations in the first two weeks after P application, likely related to microbial activity. Isotopic depletion which could result from organic P (PO) mineralization was followed by enrichment which may result from biologic discrimination in the uptake. Similar transformations were observed in both soils although transformations related to biological activity were more pronounced in the soil treated with RW. Specific P compounds were identified by the Technion group, using solution-state 31P-NMR in wastewater and in soil P extracts from Acre soils irrigated by RW and FW. Few identified PO compounds (e.g., D-glucose-6-phosphate) indicated coupled transformations of P and C in the wastewater. The RW soil retained higher P content, mainly in the labile fractions, but lower labile PO, than the FW soil; this and the fact that P species in the various soil extracts of the RW soil appear independent of P species in the RW are attributed to enhanced biological activity and P recycling in the RW soil. Consistent with that, both soils retained very similar P species in the soil pools. The HUJ group tested P stabilization to maximize the environmental safe application rates and the agronomic beneficial use of BS. Sequential P extraction indicated that the most reactive BS-P forms: WSP, membrane-P, and NaHCO3-P, were effectively stabilized by ferrous sulfate (FeSul), calcium oxide (CaO), or aluminum sulfate (alum). After applying the stabilized BS, or fresh BS (FBS), FBS compost (BSC), or P fertilizer (KH2PO4) to an alluvial soil, P availability was probed during 100 days of incubation. A plant-based bioassay indicated that P availability followed the order KH2PO4 >> alum-BS > BSC ≥ FBS > CaO-BS >> FeSul-BS. The WSPi concentration in soil increased following FBS or BSC application, and P mineralization further increased it during incubation. In contrast, the chemically stabilized BS reduced WSPi concentrations relative to the untreated soil. It was concluded that the chemically stabilized BS effectively controlled WSPi in the soil while still supplying P to support plant growth. Using the sequential extraction procedure the persistence of P availability in BS treated soils was shown to be of a long-term nature. 15 years after the last BS application to MN soils that were annually amended for 20 years by heavy rates of BS, about 25% of the added BS-P was found in the labile fractions. The UMN group further probed soil-P speciation in these soils by bulk and micro X-ray absorption near edge structure (XANES). This newly developed method was shown to be a powerful tool for P speciation in soils. In a control soil (no BS added), 54% of the total P was PO and it was mostly identified as phytic acid; 15% was identified as brushite and 26% as strengite. A corn crop BS amended soil included mostly P-Fe-peat complex, variscite and Al-P-peat complex but no Ca-P while in a BS-grass soil octacalcium phosphate was identified and o-phosphorylethanolamine or phytic acid was shown to dominate the PO fraction.

A rapid batch method was developed for the analysis of Si, Ca, Mg, and K in a large number of plant tissue samples by fusion with lithium metaborate (LiBO3) in graphite crucibles with the use of a molybdenum blue spectrophotometric analysis of silicon and FAAS for Ca, Mg, and K. Our method was tested for whole plant analysis of mature wild rice (Zizania palustris L.). Analysis of Si in plant tissue with LiBO3 in graphite crucibles is reliable and fast. Thirty-six samples can be ashed overnight, fused in one hour the next day, and analyzed for Si within approximately two hours.

Four particle-size fractions (0.045–0.075, 0.075–0.11, 0.11–0.25, and 0.50–1.00 mm sieve sizes) were used to study the relationships of bulk dissolution rates (mol g−1s−1) to particle size and measured specific surface area. All reactions were performed on sonically cleaned samples in pH 4.0, 0.01 M HOAc-LiOAc buffer at 298 K. To minimize the effects of grinding, dissolution rates were not determined until 30 days of weathering had occurred; subsequent bulk dissolution rates were still nonlinear with time and the reaction was incongruent. Bulk reaction rates were higher for the smaller particle size fractions. The rates of release of Al, Fe, and Mg were first order with respect to surface area, but the order of release for Si was 0.39. These results suggest that the direct relationship between the quantity of exposed crystalline defects and dissolution rates suggested by previous investigators does not hold true for hornblende. The surface area of hornblende grains increased 99% on average during the first 30 days of weathering, and an additional 12% during the next 29 days of weathering. Scanning electron micrographs and N2 adsorption-desorption isotherms (77 K) indicated that the formation of etch pits and hollow dissolution cores contributed to the increased surface area. High resolution TEM observations of surface materials removed by ultrasonic treatment and N2 adsorption hysteresis data suggest weathering along cleavage planes with the formation of 0.5–13 nm pores. Most of the increased adsorption of N2 in the surface area determinations, however, was due to the formation of larger etch features.

A competitive-ligand, equilibrium-dialysis technique using bromide measured methylmercury (MeHg(+)) binding to Suwannee River fulvic acid (SRFA) and NOM from a lake and a bog in Minnesota. Distribution coefficients (K(OC)) and stability constants (K') varied only slightly over a range of [Br(-)] and ratios of MeHg(+) to reduced sulfur, S(re), the putative NOM binding site. For SRFA at pH 3.0, K(OC) ranged from 10(7.7) to 10(8.2) and K' ranged from 10(15.5) to 10(16.0) over MeHg(+):S(re) ratios from 1:1220 to 1:12 200 (well below S(re) saturation). The importance of pH depends on the calculation model for binding constants. Over pH 2.98-7.62, K(OC) had little pH dependence (slope = 0.2; r(2) = 0.4; range 10(7.7)-10(9.1)), but K' calculated using thiol ligands with pK(a) = 9.96 had an inverse relationship (slope = -0.8; r(2) = 0.9; range 10(15.6)-10(12.3)). A pH-independent model was obtained only with thiol pK(a) < or = approximately 4. The mean K'(4) for SRFA (K' with thiol pK(a) = 4.2) was 10(9.8) (range 10(9.11)-10(10.27)) and small slope (0.02). Similar values were found for Spring Lake NOM; bog S2 NOM had values one-tenth as large. These constants are generally similar to published values; differences reflect variations in methods, pH, types of NOM, and calculation models.

The use of organic residues as soil additives is increasing, but, depending on their composition and application methods, these organic amendments can stimulate the emissions of CO(2) and N(2)O. The objective of this study was to quantify the effects of management practices in irrigated sweet corn (Zea mays L.) on CO(2) and N(2)O emissions and to relate emissions to environmental factors. In a 3-yr study, corn residues (CR) and pasteurized chicken manure (PCM) were used as soil amendments compared with no residue (NR) under three management practices: shallow tillage (ST) and no tillage (NT) under consecutive corn crops and ST without crop. Tillage significantly increased (P < 0.05) CO(2) and N(2)O fluxes in residue-amended plots and in NR plots. Carbon dioxide and N(2)O fluxes were correlated with soil NH(4) concentrations and with days since tillage and days since seeding. Fluxes of CO(2) were correlated with soil water content, whereas N(2)O fluxes had higher correlation with air temperature. Annual CO(2) emissions were higher with PCM than with CR and NR (9.7, 2.9, and 2.3 Mg C ha(-1), respectively). Fluxes of N(2)O were 34.4, 0.94, and 0.77 kg N ha(-1) yr(-1) with PCM, CR, and NR, respectively. Annual amounts of CO(2)-C and N(2)O-N emissions from the PCM treatments were 64 and 3% of the applied C and N, respectively. Regardless of cultivation practices, elevated N(2)O emissions were recorded in the PCM treatment. These emissions could negate some of the beneficial effects of PCM on soil properties.

Intensive cropping of Italian ryegrass (Lolium multiforum L.) in pots was used to assess the contribution of non-exchangeable K to plant uptake. The soils used were: two soils high in mica (illite) developed on recent alluvium plus two smectitic (beidellitic) soils and a soil of mixed mineralogy rich in mica. Four K treatments were used (0, 28.6, 143, and 286 mg kg-1 soil) with 8 successive monthly cuttings. A response of plant K uptake to added K was observed in all soils. Both 1.0 M NH40Ac and 0.2 M CaCl2 extractable K were depleted to a minimum level specific for each soil. The minima were lower in the old upland soils compared to the young alluvial soils. Uptake of K by Italian ryegrass induced K release from the non-exchangeable K to replenish the plant available pool of K ions. The release of mica interlayer K in the alluvial and in the high K smectitic soil supplied sufficient K to plants even under intensive cropping. The rate of mobilization of interlayer K was low in the smectitic soil with lower K. The lowest release rate was in the old high mica soil. Iron coatings may have inhibited mobilization of interlayer K. The rates of mobilization cannot be predicted from mineralogical and K-extraction data only. The rates of K uptake and the rates of K release by ryegrass under intensive cropping are potential values which can be used for modelling K availability to plants in the soils studied.

Altered surfaces of labradorite resulting from laboratory weathering at pH 4 and 25°C were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). SEM micrographs showed nonuniform surface alteration of labradorite weathered at pH 3.7 for 415 days. TEM micrographs showed exsolution lamellae of a more calcic-rich and more sodic-rich phase, each averaging approximately 700 a thick. The more calcic phase was preferentially weathered to average depths of 1350 A in excess of the more sodic phase, producing a corrugated surface. The surface roughness caused by preferential weathering of the more calcic phase affects the relative exposure of calcic and sodic phases to the XPS detector. A three-dimensional analysis of possible surface exposures was used to predict the influence of a corrugated surface on XPS measurements. Actual XPS data showed significant Ca depletion, slight Al depletion, slight Si enrichment, and slight Na enrichment relative to unweathered labradorite. Sputter depth profiling with an Ar ion gun showed that surface alteration was significant up to depths of 500 A, similar to the depth of preferential weathering of the more calcic lamellae observed with TEM. Predicted XPS data accounting for the topographic effects of a corrugated surface showed similar trends of Ca depletion, slight Al depletion, slight Si enrichment, and moderate Na enrichment. Furthermore, predicted XPS sputter depth profiles of Ca, Al, Si, and Na were similar to actual sputter depth profiles, indicating that a significant amount of the surface alteration on labradorite can be explained by preferential weathering of the more calcic lamellae, and the subsequent surface roughness effects this has on XPS spectra. Other surface processes such as H+ or H3O+ exchange for Ca, Na, or Al and preferential weathering at sites of excess surface energy (dislocations, twin boundaries, etc.) not accounted for in the predicted XPS data may also contribute to the surface composition of weathered labradorite. Results showing preferential weathering of more calcic-rich lamellae and its effect on XPS spectra indicate the importance of understanding the micro-structure of feldspars used for laboratory weathering studies.

Objectives - The overall objective of this proposal was to explore the effects of soil properties and management practices on C sequestration in soils and off-site losses of N.The specific objectives were: 1. to investigate and to quantify the effects of soil properties on C transformations that follow OW decomposition, C losses by gaseous emission, and its sequestration by organic and mineral components of the soil; 2. to investigate and to quantify the effects of soil properties on organic N mineralization and transformations in soil, its losses by leaching and gaseous emission; 3. to investigate and to quantify the effects of management practices and plants root activity and decomposition on C and N transformations; and 4. to upgrade the models NCSOIL and NCSWAP to include inorganic C and root exudation dynamics. The last objective has not been fulfilled due to difficulties in experimentally quantification of the effects of soil inorganic component on root exudation dynamics. Objective 4 was modified to explore the ability of NCSOIL to simulate organic matter decomposition and N transformations in non- and calcareous soils. Background - Rates of decomposition of organic plant residues or organic manures in soil determine the amount of carbon (C), which is mineralized and released as CO₂ versus the amount of C that is retained in soil organic matter (SOM). Decomposition rates also greatly influence the amount of nitrogen (N) which becomes available for plant uptake, is leached from the soil or lost as gaseous emission, versus that which is retained in SOM. Microbial decomposition of residues in soil is strongly influenced by soil management as well as soil chemical and physical properties and also by plant roots via the processes of mineral N uptake, respiration, exudation and decay.

A study was conducted to determine the influence of organic matter on the solubility of Al in organic soil horizons from different geographic regions. Results showed that the equilibrium solubility of Al was dependent on solution pH and the degree to which the soil organic matter was saturated with Al. Plots of Al solubility showed that, as solution pH decreased, soluble Al increased, and that, for a given pH, soluble Al increased with increasing surfacebound Al. In addition, Al solubility was always less than that predicted from the solubility of natural gibbsite or kaolinite. Temperature dependence and rate studies suggested that Al solubility was governed by an ion-exchange reaction between H* and Al and the organic matter. Aluminum solubility was similar in Oi and Oa horizon soils at the same bound aluminum ratio (BAR) and pH. No differences were noted when the soils were compared on a regional basis, suggesting that prediction of aqueous Al concentration s in organic horizons and peaty hydrologic areas could be accomplished with a simple model.

Artificial weathering of hornblende particles was conducted in buffered aqueous solutions at room temperature (25 °C) over a pH range of 3.4-4.6. Both ultrasonically cleaned starting materials and samples weathered for various periods of time (one to six months) were examined by scanning electron microscopy (SEM). Dissolution was incongruent with preferential removal of Ca, Al, Mg and Fe relative to Si. Surface weathering was discontinous. The weathered areas were uneven with preferential pitting along cleavage planes. High resolution transmission electron microscopy (TEM) showed altered hornblende with a layered structure. Smectite-like materials were removed from the weathered surfaces by sonication. It is unclear whether the smectite-like phase was a weathering product produced during the experiment or an alteration product of a mica impurity.

The chemical composition of the soil solution provides used information on the feasibllity of amending agricultural land with municipal and industrial waste, because the soil solution is the medium for most soil chemical reactions, the mobile phase in soils, and the medium for mineral absorption by plant roots. The soil solutions studied in tits research were from plots in a 4-yr field experiment conducted to evaluate the effects of the trace metals and P in sewage-sludge incinerator ash. Treatments compared ash with equivalent P rates from triple-superphosphate fertilizer and a control receiving no P application. Ash and phosphate fertilizer were applied annually at rates of 35, 70, and 140 kg citrate-soluble P ha -1 . Cognitive ash applications during 4 yr amounted to 3.6, 7.2, and 14.4 Mg ash ha -1 . Soil solutions were obtained by centrifugation-immiscible liquid displacement using a fluorocarbon displacing agent. Following chemical analysis, a chemical speciation model was used to determine possible solubility-controlling minerals for trace metals and P, and correlations between solution composition and plant uptake were analyzed. Ash increased soil solution pH, Cd, and Zn, but bad no significant effect on solution concentrations of other trace metals. Ash increased soil solution P and S, but P increases were less than those from equivalent citrate-soluble P rates of phosphate fertilizer. Soil solution Ba appeared to be in equilibrium with barite (BaSO 4 ). Solubility data did not indicate that any discrete general phases controlled Cd, Zn, Cu, Ni, Pb, or P solubility. Soil solution P concentration was strongly correlated (r=0.92) with P accumulation in sweet corn (Zea mays L.) plants, but solution trace metal concentrations were either weakly correlated (r=0.49 for Zn and 0.36 for Cd) or not significantly correlated (r=0.09 for Ni and -0.25 for Cu) with plant accumulation