Nutrient and heavy metals in decaying harvest residue needles on drained blanket peat forests

Harvest residue decomposition can significantly contribute to nutrient and heavy metal exports to receiving water courses. This study monitors the nutrient and heavy metal dynamics in decaying Sitka spruce and lodgepole pine harvest residue needles on Atlantic blanket peat forests in the west of Ireland. Using the litterbag method, harvest residue was placed both within and between furrows in two uncut forest and two clear-cut sites. On the clear-cut sites, the litterbags were positioned outside the harvest residue piles (i.e. brash windrows). Over the 2-year monitoring period, the needles decomposed slower at the clear-cut sites than the uncut forest sites, with mass losses of 46–55 and 58–77 %, respectively. Approximately 20 % less phosphorous (P) was released from the decaying needles at the clear-cut sites, while nitrogen (N) was released only at the uncut sites. Tree species was a significant factor contributing to nutrient and heavy metal release and accumulation patterns, with higher concentrations of aluminium (Al), nickel (Ni), cadmium (Cd) and zinc (Zn) in the decaying spruce needles than in pine. Conversely, the spruce needles showed accelerated depletion of calcium (Ca) and magnesium (Mg) relative to the pine. The harvest residue needle positioning (inside furrow/between furrows) and the site soil characteristics contributed significantly to Al transformations in spruce needles and iron (Fe) in both spruce and pine needles, with more accumulation occurring inside the furrows where Al and Fe contents of the peat were high. Manganese (Mn) was released from the needles in three of the four sites with a total release of over 90 % within 2 years. In the remaining site, where the Mn content of the peat was high, an accumulation of Mn in the needles was observed. The decomposition of needles on blanket peat catchments may be a significant source of P to receiving water courses, owing to their fast release of P, but not a likely source for N export.     

Use of isotope-labeled aflatoxins for LC-MS/MS stable isotope dilution analysis of foods

Aflatoxins are a group of very carcinogenic mycotoxins that can be found on a wide range of food commodities including nuts, cereals, and spices. In this study, the first LC-MS/MS stable isotope dilution assay (SIDA) for the determination of aflatoxins in foods was developed. The development of this method was enabled by easily accessible isotope-labeled (deuterated) aflatoxins B2 and G2, which were synthesized by catalytic deuteration of aflatoxin B1 and G1, purified, and well-characterized by NMR and MS. All four aflatoxins of interest (B1, B2, G1, and G2) were quantified in food samples by using these two labeled internal standards. The response factors (RF) of the linear calibrations were revealed to be matrix independent for labeled aflatoxin B2/aflatoxin B2 and labeled aflatoxin G2/aflatoxin G2. For labeled aflatoxin B 2/aflatoxin B 1 and labeled aflatoxin B2/aflatoxin G1 matrix-matched calibration was performed for the model matrices almonds and wheat flour, showing significant differences of the RFs. Limits of detection (LOD) were determined by applying a statistical approach in the presence of the two model matrices, yielding 0.31 microg/kg (aflatoxin B1), 0.09 microg/kg (aflatoxin B2), 0.38 microg/kg (aflatoxin G1), and 0.32 microg/kg (aflatoxin G2) for almonds (similar LODs were obtained for wheat flour). Recovery rates were between 90 and 105% for all analytes. Coefficients of variation (CV) of 12% (aflatoxin B1), 3.6% (aflatoxin B2), 14% (aflatoxin G1), and 4.8% (aflatoxin G2) were obtained from interassay studies. For further validation, a NIST standard reference food sample was analyzed for aflatoxins B1 and B2. The method was successfully applied to determine trace levels of aflatoxins in diverse food matrices such as peanuts, nuts, grains, and spices. Aflatoxin contents in these samples ranged from about 0.5 to 6 microg/kg.     

Phosphorus release from forest harvesting on an upland blanket peat catchment

The aim of this study was to investigate the release of phosphorus (P) to receiving waters resulting from harvesting 34-year-old lodgepole pine trees in an upland peat catchment. The study site was within a 25.3-hectare (ha) area, and was drained by a stream that received flows from ploughed furrows, mainly, via collector drains, and discharged directly to the salmonid Shrahrevagh River, Burrishoole, Co. Mayo, Ireland. The study site was divided into two parts: the upstream part was left intact and the downstream part was harvested in early Autumn 2005 following implementation of forest guidelines. Good management practices such as proper use of brash mats and harvesting only in dry weather were implemented. Two instrumented stations were established – one just upstream (US) and the other just downstream (DS) of the clearfelled area. The measurement of P concentrations at the two stations commenced in May 2005, two months before the harvesting started. The daily mean P concentration at the DS station increased from about 6 μg L⁻¹ of total reactive phosphorus (TRP) during pre-clearfelling to 429 μg L⁻¹ in August 2006. By October 2009, four years after clearfelling, the P concentrations at the DS station had returned to pre-clearfelling levels. In the first three years after harvesting, up to 5.15 kg ha⁻¹ of TRP was released from the harvested catchment to the receiving water; in the second year alone, 2.3 kg ha⁻¹ of TRP was released. Linear regression can be used to describe the relationship between TRP load and water discharge. About 80% of the total phosphorus (TP) in the study stream was soluble and more than 70% of the P release occurred in storm events, indicating that traditional buffer strips with widths of 15–20 m might not be efficient for P immobilization. The P concentrations were affected by antecedent weather conditions and highest concentrations occurred during storm events following prolonged drought periods. The water extractable phosphorus (WEP) contents in the soil were significantly higher below windrow/brash material than in brash-free areas, and whole-tree harvesting should be studied as one of the means to decrease P export from blanket peats.     

A Potential Solution to Mitigate Phosphorus Release Following Clearfelling in Peatland Forest Catchments

Since the 1950s, large areas of upland peat have been afforested in northern European countries. Due to the poor phosphorus (P) adsorption capacity and low hydraulic permeability in blanket peat soil and increased labile P sources, harvesting these blanket peat forests can significantly increase P concentrations in the receiving aquatic systems. This paper briefly reviews the current management practices on the control of P releases from forestry in Ireland and the UK, and proposes a possible novel practice??grass seeding clearfelled areas immediately after harvesting, which should reduce P release from blanket peat forest harvesting. The study was conducted in the Burrishoole Catchment in the west of Ireland. A field trial was carried out to identify the successful native grass species that could grow quickly in the blanket peat forest. The two successful grass species??Holcus lanatus and Agrostis capillaris??were sown in three blanket peat forest study plots with areas of 100, 360, and 660 m² immediately after harvesting. Areas without grass seeding were used as controls. One year later, the P content in the aboveground vegetation biomass of the three study plots were 2.83, 0.65, and 3.07 kg P?ha^?1, respectively, which were significantly higher than the value of 0.02 kg P?ha^?1 in the control areas. The water extractable phosphorus in the three study plots were 8.44, 9.83, and 6.04 mg?(kg dry soil)^?1, respectively, which were lower than the value of 25.72 mg?(kg dry soil)^?1 in the control sites. The results indicate that grass seeding of the peatland immediately after harvesting can quickly immobilize significant amounts of P and warrants additional research as a new Best Management Practice following harvesting in the blanket peatland forest to mitigate P release.     

Development of a stable isotope dilution assay for tenuazonic acid

A stable isotope dilution assay (SIDA) for the Alternaria mycotoxin tenuazonic acid was developed. Therefore, [(13)C(6),(15)N]-tenuazonic acid was synthesized from [(13)C(6),(15)N]-isoleucine by Dieckmann intramolecular cyclization after acetoacetylation with diketene. The synthesized [(13)C(6),(15)N]-tenuazonic acid was used as the internal standard for determination of tenuazonic acid in tomato products by liquid chromatography tandem mass spectrometry after derivatization with 2,4-dinitrophenylhydrazine. Method validation revealed a limit of detection of 0.1 μg/kg and a limit of quantitation of 0.3 μg/kg. Recovery was close to 100% in the range of 3-300 μg/kg. Determination of tenuazonic acid in two samples of different tomato ketchups (naturally contaminated) was achieved with a coefficient of variation of 2.3% and 4.7%. Different tomato products (n = 16) were analyzed for their content of tenuazonic acid using the developed SIDA. Values were between 15 and 195 μg/kg (tomato ketchup, n = 9), 363 and 909 μg/kg (tomato paste, n = 2), and 8 and 247 μg/kg (pureed tomatoes and comparable products, n = 5).     

Synthesis of four carbon-13-labeled type a trichothecene mycotoxins and their application as internal standards in stable isotope dilution assays

The first stable isotope dilution assay (SIDA) for the simultaneous quantitation of the most abundant type A trichothecenes in foods and feeds was developed. Synthesis of carbon-13-labeled T2-toxin, HT2-toxin, diacetoxyscirpenol, and monoacetoxyscirpenol was accomplished by [13C2]-acetylation of T2-triol and scirpentriol, respectively. Scirpentriol was prepared from diacetoxyscirpenol by complete alkaline hydrolysis and subsequently was converted to [13C6]-triacetoxyscirpentriol by peracetylation with [13C4]-acetic anhydride. The latter compound was selectively hydrolyzed using ammonium hydroxide to give [13C4]-diacetoxyscirpenol and [13C2]-monoacetoxyscirpenol in reasonable yields. Analogously, [13C6]-T2-triacetate was prepared from T2-triol and subjected to controlled hydrolysis to yield [13C4]-T2-toxin and [13C2]-HT2-toxin. All synthesized products were characterized by NMR and MS experiments. Using the prepared isotopically labeled standards, SIDAs were developed for the quantitation of type A trichothecenes in food and feeds. The mycotoxins were quantified by LC-single and tandem MS after cleanup on multifunctional columns. The method revealed good sensitivity with low detection and quantification limits along with excellent recovery and good precision in interassay studies. Food samples were analyzed using the developed SIDA and showed substantial contamination of oat products with T2-toxin and HT2-toxin. Diacetoxyscirpenol was detected on potatoes, whereas monoacetoxyscirpenol was not present in the analyzed samples.     

Concentrations of total glutathione and cysteine in wheat flour as affected by sulfur deficiency and correlation to quality parameters

A method for the simultaneous quantitation of total glutathione and total cysteine in wheat flour by a stable isotope dilution assay using high-performance liquid chromatography/tandem mass spectrometry (HPLC-MS/MS) was developed. As internal standards, L-[(13)C3, (15)N]cysteine and L-gamma-glutamyl-L-[(13)C3, (15)N]cysteinyl-glycine were used. The method consisted of the extraction and reduction of flour with tris(2-carboxyethyl) phosphine after the addition of internal standards, protection of free thiol groups with iodoacetic acid, derivatization of free amino groups with dansyl chloride, and HPLC-MS/MS. The limits of detection and quantitation for glutathione were 0.75 nmol/g and 2.23 nmol/g flour, respectively. For cysteine, the limits of detection and quantitation were 0.72 nmol/g and 2.12 nmol/g flour, respectively. The developed method was found to be sensitive enough for quantitation of total glutathione and cysteine levels in wheat flour. This method was then utilized to investigate the effect of sulfur (S) deficiency on the amount of total glutathione and cysteine in flour. In S-deficient wheat, the concentrations of total glutathione and cysteine were proportional to the amount of S supplied during growth. The calculation of correlations revealed that GSH and Cys concentrations influenced the rheological dough properties and the baking performance at least as much as protein parameters. Thus, the low concentration of GSH and Cys in flour from S-deficient wheat had a similar effect on the technological properties as the altered composition of gluten proteins.