Aluminium speciation: Variations caused by the choice of analytical method and by sample storage

We have compared a new FIA method (M1) for aluminium speciation in natural waters and a manual one based on one of Driscoll's proposals (M2). In synthetic solutions, aluminium's fluoro complexes were measured as ‘labile monomeric AP (Al _i ) by M2, but not as ‘quickly reacting Al’ (Al _qr ) by M1. Aluminium's complexes with Nordic Reference Humic Acid were measured neither as Al _i nor as Al _qr , and the same result was obtained for Al's citrato complexes. After excluding aluminium's fluoro complexes from Al _i , the results of the two methods agreed well for soil leaching samples and fairly well for natural water samples. Detection limits: 10μg L^?1 (ca. 0.4 μM) for both methods. Sample throughputs: M1∶66 injections h^?1; M2∶5 samples h^?1. Repeatabilities (RSD) on natural water samples: M1∶0.6–5.8% and M2 0.7–4.6%. Sample storage studies on soil solutions (FIA method) indicated that storage effects were ‘sample type specific’. A sample with a low level of Al _qr and a high DOC level (P2A) was more sensitive to storage than one with a high [Al] _qr and a low [DOC] (P2B^*). The decrease in [Al] _qr was statistically significant after 10 h (P2A) and 24 h (P2B^*), respectively. After 3 days' storage, [Al] _qr had decreased by some 40% in P2A, while the decrease in P2B^* was less than 10% after 8 days. The results of this part of the study also emphasize the importance of careful method standardization in sample storage studies.     

Testing Sugarbush soils: Effects of sample storage and drying

Abstract

The need for an assessment of sampling effects on forest surface soils has followed the increased interest in the fertility status of northern hardwood forests, especially sugar maple stands. We sampled soils from a fertility research site in north‐central Vermont and measured the effects of drying (55°C) and moist, low temperature storage (4°C) on extractable aluminum (Al), calcium (Ca), potassium (K), magnesium (Mg), phosphorus (P), manganese (Mn), zinc (Zn), boron (B), iron (Fe), and pH. Drying induced large, significant increases in ammonium acetate (pH 4.8) extracted P, Mn, B, and Fe. Smaller, but statistically significant, changes were found in pH, Al, Ca, and Zn. Moist storage for 10 weeks resulted in small significant changes in only pH and K. The magnitude of these changes indicate that samples can be stored at low temperature for up to 10 weeks with little effect on soil test results. Drying should be avoided because of its drastic effect on the extractability of many soil test elements.     

Aluminium speciation: comparison of two spectrophotometric analytical methods and observed concentrations in some acidic aquatic systems in Southern Norway

The toxicity of A1 to aquatic biota varies with speciation. Driscoll (1980) has developed a scheme for determining three A1 fractions using the ferron method (Smith, 1971) to detect Al. We have compared the results obtained with Driscoll's method with those obtained when pyrocatechol violet is the complexing agent. The agreement is generally satisfactory. The latter method is more sensitive and less influenced by interferences. Results for water samples, mainly from two streams in southern Norway, are discussed. For most samples the labile monomeric Al-fraction dominates, the major species being either A1³⁺ or AIF²⁺. Possible equilibria between A1³⁺ and some minerals and the temperature changes in these equilibria, are discussed.     

Frozen storage effects on anthocyanins and volatile compounds of raspberry fruit

The quantitative and qualitative evolution of the anthocyanins and volatile compounds of four raspberry cultivars (cvs. Heritage, Autumn Bliss, Zeva, and Rubi) growing in Spain were analyzed raw, just frozen, and during long-term frozen storage at -20 degrees C for a 1 year period. HS-SPME coupled with GC-MS and HPLC techniques were employed to study the evolution of the volatile compounds and the individual anthocyanins, respectively. The volatile aroma composition changes produced by the freezing process and long-term frozen storage were minimal. Only a significant increase in extraction capacity was obtained for alpha-ionone (27%) and for caryophyllene (67%) in Heritage at 12 months of storage. The stability of anthocyanins to freezing and frozen storage depends on the seasonal period of harvest. Heritage and Autumn Bliss (early cultivars) were less affected by processing and long-term frozen storage (1 year), and the total pigment extracted showed the tendency to increase 17 and 5%, respectively. Rubi and Zeva (late cultivars) suffered a decreased trend on the total anthocyanin content of 4% for Rubi and 17.5% for Zeva. Cyanidin 3-glucoside most easily suffered the degradative reactions that take place during processing and the storage period.     

Processing and storage effects on the ellagitannin composition of processed blackberry products

Changes in blackberry ellagitannin composition in response to juicing (clarified and nonclarified), pureeing, canning (in water or syrup), and freezing as well as changes in processed products during 6 months of storage were investigated. Canning, pureeing, and freezing had little effect on ellagitannins, but processing berries into nonclarified and clarified juices resulted in total ellagitannin losses of 70 and 82%, respectively, due to removal of ellagitannin-rich seeds in the presscake. Minimal changes in total ellagitannin content were observed during storage of thermally processed products, but compositional changes indicative of ellagitannin depolymerization were apparent. The ellagitannin content and composition of frozen berries remained stable over 6 months of storage. Ellagitannins are well retained in canned, pureed, and frozen blackberries, but methods are needed to prevent losses during juice processing and/or exploit the ellagitannin-rich coproducts.     

Processing and storage effects on orange juice aroma: a review

Freshly squeezed orange juice aroma is due to a complex mixture of volatile compounds as it lacks a specific character impact compound. Fresh hand-extracted juice is unstable, and thermal processing is required to reduce enzyme and microbial activity. Heating protocols range from the lightly heated not from concentrate, NFC, to the twice heated, reconstituted from concentrate, RFC, juices. Thermal processing profoundly effects aroma composition. Aroma volatiles are further altered by subsequent time-temperature storage conditions. Heating reduces levels of reactive aroma impact compounds such as neral and geranial, and creates off-flavors or their precursors from Maillard, Strecker, and acid catalyzed hydration reactions. Off-flavors such as 4-vinylguaiacol, p-cymene, and carvone are the products of chemical reactions. Other off-flavors such as butane-2,3-dione, guaiacol, and 2,6-dichlorophenol are indicators of microbial contaminations. Since most orange juice consumed worldwide is processed, the goal of this review is to summarize the widely scattered reports on orange juice aroma differences in the three major juice products and subsequent aroma changes due to packaging, storage, and microbial contamination with special emphasis on results from GC-O studies.     

Genetic evidence for speciation in <Emphasis Type="Italic">Cannabis</Emphasis> (Cannabaceae)

Sample populations of 157 Cannabis accessions of diverse geographic origin were surveyed for allozyme variation at 17 gene loci. The frequencies of 52 alleles were subjected to principal components analysis. A scatter plot revealed two major groups of accessions. The sativa gene pool includes fiber/seed landraces from Europe, Asia Minor, and Central Asia, and ruderal populations from Eastern Europe. The indica gene pool includes fiber/seed landraces from eastern Asia, narrow-leafleted drug strains from southern Asia, Africa, and Latin America, wide-leafleted drug strains from Afghanistan and Pakistan, and feral populations from India and Nepal. A third putative gene pool includes ruderal populations from Central Asia. None of the previous taxonomic concepts that were tested adequately circumscribe the sativa and indica gene pools. A polytypic concept of Cannabis is proposed, which recognizes three species, C. sativa, C. indica and C. ruderalis, and seven putative taxa.     

Instability of phosphate during storage and shaking of gülle

Gülle samples were unstable during both storage and experimentation. Phosphate concentrations in solution decreased quite sharply during the first month of storage at either 4°C or laboratory temperature, and thereafter continued to decrease at a slower rate until pseudoequilibrium was reached after 80–100 days.     

Rhizosphere reactions of Aluminium and manganese

Some aspects of the forms and reactions of Al and Mn in the rhizosphere of plants are discussed in relation to Mn availability and Al toxicity. The differences in behaviour between the two elements are sufficiently great that quite distinctly different procedures are required to estimate availability of Mn and toxicity of Al.     

Effect of Aluminium on Microbial Respiration

Aluminium is a non-essential element for biological systems and is used in water and wastewater processes that rely on (micro)biological purification processes. The effect of Al doses ranging from 100 to 2,000 μg/l on the microbial dissolved oxygen uptake (respiration) over a 24-h period was assessed. Results indicated that Al can reduce the 24-h respiration, but the effects of pH depression due to Al dosing during testing should be taken into account.     

Modeling the effects of climatic and co2 changes on grassland storage of soil C

We present results from analyses of the sensitivity of global grassland ecosystems to modified climate and atmospheric CO₂ levels. We assess 31 grassland sites from around the world under two different General Circulation Models (GCM) double CO₂ climates. These grasslands are representative of mostly naturally occurring ecosystems, however, in many regions of the world, grasslands have been greatly modified by recent land use changes. In this paper we focus on the ecosystem dynamics of natural grasslands. The climate change results indicate that simulated soil C losses occur in all but one grassland ecoregion, ranging from 0 to 14% of current soil C levels for the surface 20 cm. The Eurasian grasslands lost the greatest amount of soil C (～1200 g C m^?2) and the other temperate grasslands losses ranged from 0 to 1000 g C m^?2, averaging approximately 350 g C m^?2. The tropical grasslands and savannas lost the least amount of soil C per unit area ranging from no change to 300 g C m^?2 losses, averaging approximately 70 g C m^?2. Plant production varies according to modifications in rainfall under the altered climate and to altered nitrogen mineralization rates. The two GCM's differed in predictions of rainfall with a doubling of CO₂, and these differences are reflected in plant production. Soil decomposition rates responded most predictably to changes in temperature. Direct CO₂ enhancement effects on decomposition and plant production tended to reduce the net impact of climate alterations alone.     

Solubility and speciation of zinc in calcareous soils

Water, Air, & Soil Pollution - The objective of this study was to evaluate the formation of a probable Zn solid phase in soils. Thermodynamic solubility isotherms revealed that ZnFe2O4, Zn2SiO4...     

Flavonoid and carbohydrate contents in Tropea red onions: effects of homelike peeling and storage

The content of anthocyanins, flavonols, and carbohydrates of Tropea red onions (Allium cepa L.) was determined by HPLC and HPLC-MS. Cyanidin derivatives constitute >50% of total anthocyanins, but delphinidin and petunidin derivatives, which have not been reported in red onions thus far, were also detected. The flavonoid distribution in the different layers of the bulbs indicates that, after homelike peeling, the edible portion contains 79% of the total content of quercetin 4'-glucoside but only 27% of the anthocyanins. Storage of onions for 6 weeks in different conditions, all of them mimicking home storage habits, resulted in a decrease to 64-73% of total anthocyanins. The same trend was verified for the total antioxidant activity, which was reduced to 29-36%. A decrease in glucose and fructose content correlated with anthocyanin degradation was also observed. Storage at low temperature seems to better preserve the onion anthocyanins.     

Computer‐based evaluation of methods to sample nitrate leached from grazed pasture

Scientists, land managers and environmental regulators all want to quantify the amount of nitrate leached into groundwater to better understand and manage the risk of environmental contamination from agricultural land, including grazed pasture. The ability of current technology to adequately measure the nitrate leached from a grazed paddock is tested in a stochastic simulation study. Results show that impractical numbers of samplers are needed to achieve estimates accurate to within ±20% of the true value. Rather than trying to directly measure paddock‐scale leaching under grazing, we suggest that further consideration be given to wider application of controlled application of nitrogen onto a few lysimeters and then extrapolate from the resulting measurements of leached nitrate to the paddock scale and beyond based on urine patch coverage.     

Metal speciation: Survey of environmental methods of analysis

As part of a recent task under the EPRI Analytical Methods Qualification Program (RP 1851), TRW has surveyed the methods available for monitoring metal species in typical utility aqueous discharge streams. Methods for determining the individual species of these metals can become important in a regulatory sense as the EPA transitions to assessment of environmental risk based on bioavailability. For example, EPA considers methyl mercury and Cr(VI) much more toxic to the aquatic environment than inorganic mercury or Cr(III). The species of a given element can also differ in their transport and bioaccumulation. Methods for speciation generally include a selective separation step followed by standard metals analysis. Speciation, therefore, is mainly derived from the separation step and not from the method of final quantitation. Examples of separation/analysis include: selective extraction followed by graphite furnace atomic absorption or ICP-MS; separation by GC followed by metals detection; chelation and/or direct separation by LC followed by UV measurement or metals detection; and ion chromatography with conductivity, UV, or metals detection. There are a number of sampling issues associated with metal species such as stabilization (maintaining oxidation state), absorption, and filtration that need to be addressed in order to obtain and maintain a representative sample for analysis.     

Results of the international aqueous mercury speciation intercomparison exercise

Twenty-seven laboratories from around the world agreed to participate in an intercomparison exercise for total Hg (Hg_t) and methyl Hg (MMHg) in pristine lake water. Unfiltered samples from a remote brown water lake in northern Wisconsin (USA) were collected into acid cleaned Teflon^® bottles using ultra-clean sample handling techniques. The samples were acidified in the field with 0.4% by volume of pre-analyzed HCl (12N; <5 pg Hg/mL), and sent to the primary reference laboratory (PRL) by overnight mail. Within one week of receipt, the samples were randomized, and 10% analyzed for Hgt and MMHg at the PRL to verify the homogeneity of the set. Each participating laboratory was then sent 3 randomly selected 1 L bottles, while the PRL retained 30, and the secondary reference laboratory (SRL) retained 12 samples. The participating laboratories were asked to analyze each bottle in triplicate for both Hgt and MMHg, reporting all QA data including blanks, spike recoveries, and detection limits. The PRL analyzed samples in triplicate at both the beginning and the end of the analytical window, to provide a controlled estimate of any changes in concentration or speciation over that time. Of the 23 laboratories that returned results, 18 utilized BrCl oxidation, gold trapping, and cold vapor atomic fluorescence (CVAFS) detection for Hg_t. Four laboratories reported similar techniques, varying either in detector (cold vapor atomic absorption), or wet chemistry. Only 16 laboratories reported MMHg results, with 15 using a variation of the aqueous phase ethylation, GC separation, and CVAFS detection technique. The results show good convergence between the participating labs for both Hg_t and MMHg. For Hgt 18 of 23 labs reported means within 20% of the consensus value and PRL results (1.27±0.18 ng/L and 1.27±0.14 ng/L respectively). For MMHg, 13 of the 16 labs reported results within 20% of either the consensus value (0.420±0.055 ng/L) or the PRL value (0.446±0.041 ng/L).     

Sulphate supply and its effects on sap quality during growth in sugar beet storage roots

Increasing the concentration of inorganic N increases the concentration of α-amino-N compounds in roots of hydroponically-grown sugar beet plants. These concentrations can, however, be reduced by increasing the concentration of sulphate in the nutrient solution.     

Interactive effects of duration of storage and addition of formaldehyde on levels of aflatoxin M1 in milk

Spray-dried skim milk, naturally contaminated with aflatoxin M1, was added to either raw or pasteurized whole milk to a final concentration of 1.1 microgram aflatoxin M1/L milk. Formalin (37% w/w) was added to the milk solutions to final concentrations of 0, 0.025, 0.05, and 0.1% formaldehyde. Samples were stored in the dark at 21 degrees C in plastic and glass containers and were analyzed for aflatoxin M1 at 0, 1, 2, 3, and 4 weeks. This experiment was repeated using only raw milk and glass containers. Aflatoxin M1 analyses were done at 0, 1, and 2 weeks. Aflatoxin M1 losses increased over time and with increased formaldehyde concentration. With both experiments, aflatoxin M1, levels after 2 weeks were less than 0.05 micrograms/L in samples containing 0.1% formaldehyde.     

Uptake, Deposition and Wash Off of Fluoride and Aluminium in Plant Foliage in the Vicinity of an Aluminium Smelter in Norway

Uptake, deposition and wash off of fluoride and aluminium in/on plant foliage were studied in two experiments near an Al smelter by growing different plant species under cover with free wind-flow underneath, and in the open, and by washing the leaves. With an average ambient air concentration of 2.2 μg F m³, the F and Al contents in leaves varied between species from 138 to 665 mg F kg^?1 and from 150 to 1025 mg Al kg^?1when grown under cover. An average of about 60% of the F and nearly 70% of the Al could be washed off covered plants. Uncovered plants had 33–51% lower F content, indicating a considerable precipitation wash off. Precipitation wash off varied with species, probably due to different leaf surface properties. The strong effect of precipitation on plant foliage F has to be taken into consideration when comparing differences in F content between years, localities and species. On average about 40–50% of the F and 55% of the Al could be washed off the leaves of uncovered plants. Washed leaves of plants exposed to precipitation had about 20% lower F content, compared to washed leaves of covered plants, thus indicating leaching of F from leaves exposed to rain. In contrast to fluoride, the Al contents in washed leaves of uncovered plants were about 50–80% higher than in covered washed leaves, thus indicating a significant uptake of Al solved in rainwater through the leaf cuticle.     

Cytochrome oxidase as an indicator of ice storage and frozen storage

The potential of cytochrome oxidase as an indicator of ice storage and frozen storage of fish was investigated. Optimal assay conditions for cytochrome oxidase in a crude homogenate from cod muscle were studied. Maximal cytochrome oxidase activity was found at pH 6.5-7.5 and an assay temperature of 30 degrees C. Maximal activation by Triton X-100 was obtained in a range of 0.62-1.25 mM Triton X-100. The specificity of the assay was high, as cytochrome oxidase was inhibited 98% by 33 microM of the specific inhibitor sodium azide. The coefficient of variation of cytochrome oxidase activity in different cods was 21%, and the coefficient of variation of different analyses on the same homogenate was 5%. It was shown that ice storage of muscle samples before they were frozen and thawed resulted in a major freezing-induced activation of cytochrome oxidase activity. The enzyme may therefore be used as an indicator of frozen fish to determine if the fish has been stored on ice before freezing. Cytochrome oxidase activity showed also potential as an indicator of frozen storage, as it was possible to distinguish between the frozen storage temperatures -9, -20, and -40 degrees C.