Characterization of phosphorus species in biosolids and manures using XANES spectroscopy

Identification of the chemical P species in biosolids or manures will improve our understanding of the long-term potential for P loss when these materials are land applied. The objectives of this study were to determine the P species in dairy manures, poultry litters, and biosolids using X-ray absorption near-edge structure (XANES) spectroscopy and to determine if chemical fractionation techniques can provide useful information when interpreted based on the results of more definitive P speciation studies. Our XANES fitting results indicated that the predominant forms of P in organic P sources included hydroxylapatite, PO(4) sorbed to Al hydroxides, and phytic acid in lime-stabilized biosolids and manures; hydroxylapatite, PO(4) sorbed on ferrihydrite, and phytic acid in lime- and Fe-treated biosolids; and PO(4) sorbed on ferrihydrite, hydroxylapatite, beta-tricalcium phosphate (beta-TCP), and often PO(4) sorbed to Al hydroxides in Fe-treated and digested biosolids. Strong relationships existed between the proportions of XANES PO(4) sorbed to Al hydroxides and NH(4)Cl- + NH(4)F-extractable P, XANES PO(4) sorbed to ferrihydrite + phytic acid and NaOH-extractable P, and XANES hydroxylapatite + beta-TCP and dithionite-citrate-bicarbonate (DCB)- + H(2)SO(4)-extractable P (r(2) = 0.67 [P = 0.01], 0.78 [P = 0.01], and 0.89 [P = 0.001], respectively). Our XANES fitting results can be used to make predictions about long-term solubility of P when biosolids and manures are land applied. Fractionation techniques indicate that there are differences in the forms of P in these materials but should be interpreted based on P speciation data obtained using more advanced analytical tools.     

Uptake and bioavailability of persistent organic pollutants by plants grown in contaminated soil

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of endosulfan compounds from slurry spiked soil (10, 20 and 40 microg g(-1)) was consistent (92.9 +/- 4.4% for n= 9). However, ageing of endosulfan compounds on the slurry spiked soil resulted in lower recoveries (average losses were 12.5% after 14 days ageing of slurry spiked soil). The uptake of POP's was assessed by measuring the amount of endosulfan compounds in roots and leaves from lettuce plants after 10, 20 and 33 days. In addition, control plants grown in uncontaminated soil were monitored and analysed. It was found that endosulfan compounds were present in the roots of all lettuce plants irrespective of soil spike level or age of plant. In the 33 day lettuce plants where the soil was spiked at the highest level (50 microg g(-1)) endosulfan compounds were determined in the leaves. The root to leaf ratio was found to be 3.1 for alpha-endosulfan, 46.0 for beta-endosulfan, and 24.3 for endosulfan sulfate. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of endosulfan compounds. No detectable endosulfan compounds were determined in the gastric extracts while small quantities (range 0.06-0.12 microg g(-1)) were found in the intestinal extraction. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection.     

Constructive controversy,the Vroom-Yetton model,and managerial decision-making

Empirical tests have indicated that following the Vroom-Yetton Normative Model of leadership predicts reliably to successful managerial decision-making. However, it does not consider the kind of social interaction among decision makers. Recent experiments have demonstrated that controversy constructively discussed can facilitate decision-making. To see whether constructive controversy can supplement the Vroom-Yetton model, 58 managers enrolled in an executive-level MBA programme described a successful and unsuccessful decision-making experience by answering the Vroom-Yetton questions and by indicating the extent those involved in making the decision experienced constructive controversy. Results indicate that both the Vroom-Yetton model and constructive controversy are significantly related to successful decision-making. A regression analysis indicated that constructive controversy accounted for 45 per cent of the variance of decision success whereas the Vroom-Yetton model accounted for 5 per cent. While the Vroom-Yetton model is useful at the preplanning stage for choosing a decision style, much greater contribution is provided by constructive discussions of opposing opinions when actually generating the decision.     

South Africa's arid and semiarid rangelands: Why are they changing and can they be restored?

Since the mid-19th century settled livestock ranching has been the major form of land use in South Africa, occupying 68% of the land surface. Decreases in livestock densities and ranch numbers during the past century imply that carrying capacities for domestic herbivores are falling. Differences in carbon isotope signals with soil depth and abrupt shifts in dominant plant species across ranch boundaries reveal that southern African rangelands are changing. Case studies suggest ways to control altered grassland composition, bush encroachment in arid savanna, and dominance by toxic and halophytic shrubs in arid shrublands. But climatic and biological factors constrain rates of passive recovery, and guidelines for active restoration are poor and techniques costly. Moreover, conservation of remaining good rangeland is seldom enforced, and economic considerations usually outweight the land user's desire to sustain diversity and productivity.     

Influence of solvent and soil type on the pressurised fluid extraction of PAHs

Pressurised fluid extraction (PFE) of polycyclic aromatic hydrocarbons (PAHs) from a certified reference material (CRM) 524 has been firstly optimised following a central composite design. The instrumental parameters of the PFE (pressure, temperature, extraction time and number of solvent cycles) were studied in order to obtain maximum extraction yields. Neither pressure nor extraction time or temperature seemed to have any significant effect on the extraction yield, therefore one extraction cycle was enough to exhaustively extract all the PAHs from CRM 524. Once the instrumental conditions were established, the extraction yields obtained with eight different solvents or solvent mixtures [acetone, dichloromethane, acetonitrile, acetone-dichloromethane (1 + 1 v/v), acetone-isohexane (1 + 1 v/v), isohexane, methanol and toluene] from the CRM 524 were compared and showed that the best recoveries were obtained with acetone-isohexane (1 + 1 v/v). Finally, the effect of sand, silt, clay and the organic matter content of soil was investigated with respect to recovery of PAHs by PFE with different solvents or solvent mixtures for aged soil samples. In this case, eight soils with different sand, silt, clay and organic matter contents were slurry spiked with PAHs and aged for 19 days. Three aliquots of each slurry spiked soil were extracted with the previously mentioned solvents and the results were studied by means of principal component analysis (PCA) of the whole data set (soil composition, solubility parameter of the solvent and recoveries of all PAHs) and partial least squares (PLS). Clay and organic matter content and the squared solubility parameter have the highest correlation with the recovery of PAHs from soil samples.     

Genetic structure of the southeastern United States loggerhead turtle nesting aggregation: evidence of additional structure within the peninsular Florida recovery unit

The southeastern United States supports one of two large loggerhead turtle (Caretta caretta) nesting aggregations worldwide and is therefore critical to global conservation and recovery efforts for the species. Previous studies have established the presence of four demographically distinct nesting populations (management units) corresponding to beaches from (1) North Carolina through northeastern Florida, (2) peninsular Florida, (3) the Dry Tortugas, and (4) northwest Florida. Temporal and geographic genetic structure of the nesting aggregation was examined utilizing partial mitochondrial control region haplotype frequencies from 834 samples collected over the 2002 through 2008 nesting seasons from 19 beaches as well as previously published haplotype data. Most rookeries did not exhibit interannual genetic variation. However, the interannual variation detected did significantly impact the interpretation of spatial genetic structure in northeastern Florida. Based on pairwise F _ST comparisons, exact tests of population differentiation, and analysis of molecular variance, the present study upholds the distinctiveness of the four currently recognized management units and further supports recognition of discrete central eastern, southern (southeastern and southwestern), and central western Florida management units. Further subdivision may be warranted, but more intensive genetic sampling is required. In addition, tools such as telemetry and mark-recapture are needed to complement genetic data and overcome limitations of genetic markers in resolving loggerhead turtle rookery connectivity in the southeastern USA.     

Determination of chemical characterizations of activated carbons from various raw materials

The objectives of this research were to identify the surface chemical features of activated carbons made of peat, bituminous coal and coconut shell, as well as examine the specific relationship of these properties by using statistical analyses. The results showed that the peat carbons contained much more amounts of Ca, S, P and Mg; however, the bituminous carbons possessed higher contents of Si, Al and Fe. In addition, the content ratios of Al to Si exhibited the Al enrichment phenomenon occurred after the heat treatment. A nonlinear correlation between the pH value and the difference in the amounts of basic and acidic groups was developed. Unfortunately, there were no specific mass ratios found among the acidic functional groups. The results of correspondence analysis (CA) gave a promising confirmation about the EDXRF analysis; moreover, the results of factor analysis (FA) fairly agreed with the findings suggested by CA. Both could explain the specific chemical features of activated carbons made from different materials, especially the CA could differentiate each other in detail.     

Assessment of mutagenic potency of source water treated by ozone and adsorption processes

This research utilized the Ames test to determine the mutagenicity of water treated by advanced processes, including ozonation and granular activated carbon (GAC). Raw water samples for this research included those obtained from the Pan Hsin waterworks as well as samples containing humic acids. Treated samples were collected from the pilot‐scale advanced treatment plant. The Ames test was used to measure the mutagenicity of the water after each treatment process. For the Pan Hsin raw water samples treated with ozone or GAC, it was indicated that, regardless of whether samples were preozonated or not, they all showed a mutagenic potency less than 2 once the S9 enzyme was added. This level of mutagenicity is insignificant. The prepared humic acid samples, on the other hand, demonstrated a significant reduction in mutagenicity after the pre‐ozonation process, indicating that preozonation can lower the degree of mutagenicity. Furthermore, the mutagenicity of the prepared humic acid samples gradually decreased after the advanced treatment process. However, when chlorine was added later to these samples, the mutagenicity increased again. This research shows that the use of O3/GAC processes to treat water can successfully lower mutagenicity, indicating a great potential for applications in the treatment of drinking water.     

Adsorption Characteristics of Benzene on Biosolid Adsorbent and Commercial Activated Carbons

Abstract

This study selected biosolids from a petrochemical waste-water treatment plant as the raw material. The sludge was immersed in 0.5-5 M of zinc chloride (ZnCl₂) solutions and pyrolyzed at different temperatures and times. Results indicated that the 1-M ZnCl₂-immersed biosolids pyrolyzed at 500 °C for 30 min could be reused and were optimal biosolid adsorbents for benzene adsorption. Pore volume distribution analysis indicated that the mesopore contributed more than the macropore and micropore in the biosolid adsorbent. The benzene adsorption capacity of the biosolid adsorbent was 65 and 55% of the G206 (granular-activated carbon) and BPL (coal-based activated carbon; Calgon, Carbon Corp.) activated carbons, respectively. Data from the adsorption and desorption cycles indicated that the benzene adsorption capacity of the biosolid adsorbent was insignificantly reduced compared with the first-run capacity of the adsorbent; therefore, the biosolid adsorbent could be reused as a commercial adsorbent, although its production cost is high.     

Evidence for seasonal mate limitation in populations of an intertidal amphipod, Corophium volutator (Pallas)

Potential rates of reproduction (PRR) differ between the sexes of many animal species. Adult sex ratios together with PRR are expected to determine the operational sex ratio (OSR) defined as the ratio of fertilizable females to sexually active males at any given time. OSR is expected to determine the degree to which one sex competes for another—the limiting sex. We explored the potential for mate limitation in an intertidal amphipod, Corophium volutator (Pallas). Males have higher PRR than females, but males may be limiting because of extreme female-biased sex ratios observed in this species. Consistent with this idea, late season females were less likely to be ovigerous and had smaller size-specific clutches, both of which were associated with seasonal declines in availability of males of reproductive size. Seasonal changes in ovigery could not be explained by seasonal changes across sites in other factors (e.g., female body size or phenology of breeding). Smaller females were less likely to become ovigerous later in the season at three of four sites. Seasonal reductions in clutch size also occurred among small females expected to be reproducing for their first time. In complimentary laboratory experiments, reduced likelihood of ovigery and reduced fecundity occurred when the number of receptive females was increased relative to availability of a reproductively active male. Our results suggest male mate limitation can occur seasonally in this species and that male limitation is regionally widespread and may affect recruitment.