Fumonisin mycotoxins in human hair

This study shows for the first time the accumulation of fumonisin mycotoxins in human hair of population clusters exposed to contaminated maize, and thus the feasibility of human hair analysis for the assessment of past fumonisin exposure. Composite hair samples were obtained from the Bizana, Butterworth and Centane districts within the Transkei region of the Eastern Cape Province of South Africa. Following methanol extraction and strong anion exchange clean up, the fumonisins FB₁, FB₂ and FB₃ were detected using high performance liquid chromatography coupled to electrospray ionization-mass spectrometry (HPLC-ESI-MS). Hair from Centane and Butterworth showed mean levels of FB₁ of 26.7 and 23.5 μg kg^?1 hair, respectively. FB₂ was only detected in hair from Centane and in one sampling point in Butterworth, with mean levels of 6.5 and 5.7 μg kg^?1 hair, respectively. Hair samples from Bizana, on the other hand, were found to contain higher levels of FB 1 (mean 33.0 μg kg^?1 hair) and FB 2 (mean 11.1 μg kg^?1 hair). No samples contained more than trace levels of FB 3 . Recoveries from spiked hair samples using this method ranged from 81% to 101%, demonstrating the applicability of hair analysis in assessing human exposure to fumonisin mycotoxins.     

Effects of oral administration of aflatoxin B1 and fumonisin B1 in rabbits (Oryctolagus cuniculus)

The effects of prolonged oral administration (21 days) of fumonisin B₁ (FB₁) and aflatoxin B₁ (AFB₁) were studied in male New Zealand rabbits by clinical, pathological, biochemical and sphingolipid analyses. Twenty-four animals were randomly divided into the following four experimental groups: (A) 0 mg FB₁ + 0 μg AFB₁/(kg body weight (bw) day) (control); (B) 0 mg FB₁ + 30 μg AFB₁/(kg bw day); (C) 1.5 mg FB₁/(kg bw day) + 30 μg AFB₁/(kg bw day); (D) 1.5 mg FB₁/(kg bw day) + 0 μg AFB₁. Animals from group B and principally from group C presented clinical signs of intoxication. Rabbits from group C presented a lower body weight gain than controls. Differences were observed between intoxicated rabbits and controls with respect to absolute and relative liver and kidney weight, hepatic function, serum urea and creatinine levels and Sa/So ratio. The most frequent hepatic and renal injuries were vacuolar degeneration of the liver and kidney as shown by the histopathological and serum biochemical results. Combined administration of AFB₁ and FB₁ resulted in synergistic toxic effects both in the liver and in the kidney, but hepatic injuries were more marked.     

Biological activities of synthetic analogues of Alternaria alternata toxin (AAL-toxin) and fumonisin in plant and mammalian cell cultures

In a search for an analogue of AAL-toxin with high phytotoxicity and low mammalian toxicity, aminopentols [(AP₁), hexacetyl AP₁ and N-acetyl AP₁], and nine analogues (1–9), were tested for toxicity to duckweed (Lemna pausicostata), susceptible tomato (asc/asc) leaf discs, black nightshade leaf discs and mammalian cell lines, including dog kidney (MDCK), rat liver hepatoma (H4TG) and mouse fibroblasts (NIH3T3). These were compared with AAL-toxin and fumonisin B₁ (FB₁). Analogue 9 at 10 μM increased cellular leakage and chlorophyll loss from both tomato and black nightshade leaf discs. The diester 9 was the most active in the duckweed bioassay, but it was much less toxic to MDCK and H4TG cells with an IC₅₀ of 200 μM compared to 10 μM for FB₁. Analogue 9 and FB₁ showed similar low toxicities (IC₅₀ = 150 μM) to NIH3T3 cells. Among the substances tested, only analogue 9 had significant phytotoxicity and low mammalian toxicity, indicating some potential for development of safe and effective natural herbicides.     

Bioherbicidal effect of fumonisin B1, a phytotoxic metabolite naturally produced by Fusarium nygamai, on parasitic weeds of the genus Striga

Fusarium nygamai has been isolated and identified from diseased Striga hermonthica plants collected from sorghum fields in the Sudan. Fumonisin B₁, produced by this fungus, was isolated and purified. In in vitro experiments, the bioherbicidal potential of this mycotoxin was evaluated against S. hermonthica and S. asiatica. Different concentrations (250, 500 and 1000 μg L^-1 of water) of fumonisin B₁, applied during the conditioning phase of the Striga seeds significantly reduced the germination of both species in a range of 19.8-32.2 and 34.5-47.6%, respectively. In addition, the length of the germ tubes was reduced and the germ tubes became brownish. Fumonisin B₁ slightly delayed the emergence of Striga when 250 mg fumonisin B₁ dissolved in 1 L of water were applied into the soil per pot before sowing sorghum. By the way of contrast, fumonisin B₁ was very phytotoxic when Striga seedlings (leaves and stems) of different heights and ages were sprayed with a concentration series of 250, 500 and 1000 μg fumonisin B₁ mL^-1 until run-off, or when plants were injured with a scalpel before fumonisin B₁ was applied into the injury at concentrations of 250 and 500 μg mL^-1. One day after application, the plants showed symptoms of wilting, first at the top and then moving downwards. Leaves turned black and stems desiccated at the point of injuries. Within 4 days after the application, 55% of the plants tested were completely destroyed. In total, at the end of the experiment, 40 days after the treatment, 85% of the treated plants were killed by fumonisin B_1, regardless of the concentration applied and the application technique used.     

Oxidative stress induced by fumonisin B1 in continuous human and rodent neural cell cultures

Fumonisin B₁ (FB₁) is a mycotoxin produced by Fusarium verticillioides, which is a common infectant of corn and other cereal grains. Of concern to human health is also a possible airborne exposure to FB₁-producing strains of F. verticillioides, which may grow in moisture-damaged buildings. In this study, we have characterized oxidative stress-related parameters induced by FB₁ in three different neural cell lines, human SH-SY5Y neuroblastoma, rat C6 glioblastoma and mouse GT1-7 hypothalamic cells. The cells were exposed to graded doses of FB₁ between 0.1 and 100 μM for 0-144 h after which the production of reactive oxygen species (ROS), lipid peroxidation, intracellular glutathione (GSH) levels and cell viability were measured. FB₁ caused a dose-dependent increase of ROS production in C6 glioblastoma and GT1-7 hypothalamic cells but was without an effect in SH-SY5Y cells. Decreased GSH levels, increased MDA-formation, indicative of lipid peroxidation and necrotic cell death were observed in all cell lines after incubation with FB₁. These findings indicate that FB₁ induces oxidative stress in human, rat and mouse neural cell cultures.     

The determination of fumonisin B1 in human faeces: a short term marker for assessment of exposure

Fumonisin B₁ (FB₁) is a compound that occurs frequently in rural foods and feeds, creating health hazards. When ingested, FB₁ does not appear to change in structure and is mostly excreted unchanged in faeces within 24 h. Twenty human stool samples obtained from rural school children of Vulamehlo, south of Durban (South Africa), were analysed for FB₁, as well as 23 urban control samples obtained from various households within the Durban metropolitan area. The samples were freeze-dried and ground to a fine powder. A fraction of each sample was extracted three times with aqueous ethylenediaminetetraacetic acid at pH 5.2. The pooled extracts were purified using reversed phase C₁₈ solid phase extraction cartridges. Analytical high performance liquid chromatography was used to quantitate the amount of FB₁ as an o-phthaldialdehyde (OPA) derivative in the extracts. The rural (35%) and the urban samples (9%) showed the presence of FB ranging from 790 to 19 560 ng g^-1 of freeze dried stool. It was concluded that this method could be used as a routine biomarker for short term human exposure to FB₁ in contaminated food.     

添加秸秆和磷素对土壤微生物群落的影响

为了探讨添加小麦秸秆和磷素对低磷土壤微生物数量和群落结构的影响,设置2个梯度的小麦秸秆添加量(N₀和N₁分别为0和2.08 g·kg^-1)和4个施磷水平(P₀、P₁、P₂和P₃分别为0、100、200和400 mg·kg^-1)组合处理,采用磷脂脂肪酸(PLFA)法测定土壤微生物生物量.结果表明: 添加秸秆配合施入磷素对微生物总生物量、细菌生物量、真菌生物量和真菌/细菌(F/B)比值具有显著的促进作用,微生物总生物量、细菌生物量、真菌生物量和F/B均为N₁P₁>N₁P₀>N₁P₂>N₁P₃>N₀P₁>N₀P₂>N₀P₃.在相同磷素水平下,添加秸秆处理的各指标均显著高于未添加秸秆处理;在添加相同秸秆量条件下,施磷处理的各指标随磷素施入量先增加后降低,以P₁水平组合最优,其次是P₀,最后是P₂和P₃.     

Formation and persistence of N7-methylguanine DNA adducts in the target pyloric tissue following chronic exposure to N-methyl-N'-nitro-N-nitrosoguanidine

Outbred 7-week old male Wistar rats were exposed for 21 days to N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) via the drinking water and N7-methyl deoxyguanosine 3'-monophosphate (N7-MedGp) levels in DNA from the pyloric mucosa (target tissue) and white blood cells (wbc: non-target tissue) were determined by ³²P-postlabelling. Exposure to MNNG resulted in the non-linear, dose-related formation of N7-medGp in both tissues. Adduct levels in the pyloric mucosa were determined to be 1058, 5.4 and 1.1 μmole N7-medGp mole^-1 deoxyguanosine 3'-monophosphate (dGp) after exposure to 4.1, 0.62 and 0.006 mg MNNG kg^-1 day^-1 respectively whereas adduct levels in the wbc DNA were lower at 5.2, 0.52 and 0.68 μmoles N7-medGp mole^-1 dGp after exposure to 4.1, 0.62 and 0.062 mg MNNG kg^-1 day^-1 respectively. In addition, the persistence of N7-medGp was investigated. Loss of adduct occurred rapidly, with a decrease of 87 and 97% respectively in target tissue and wbc DNA by 48 h after cessation of 4.1 mg MNNG kg^-1 day^-1 exposure; 14 days post-MNNG treatment, however, N7-medGp was still detectable (0.46 μmole N7-medGp mole^-1 dGp) in pyloric mucosal DNA. The quantitation of N7-medGp after exposure to low doses of carcinogen, i.e. 0.006 mg MNNG kg^-1 day^-1, approaching environmentally relevant levels has not been previously reported, and indicates that the ³²P-postlabelling assay developed here possesses sufficient sensitivity to quantitate N7- medGp in human DNA arising from environmental exposure to methylating agents.     

Hepatic CYP1A induction in rainbow trout (Oncorhynchus mykiss) after exposure to benzo[a]pyrene in water

Juvenile rainbow trout were exposed to unlabelled benzo[a]pyrene BaP and ³H benzo a pyrene (³H BaP), in a static exposure system for 2 days. The initial concentration was 30 μg l^-1 and 0.625 μCi l^-1, corresponding to 6 mg kg^-1 body weight and 125 μCi kg^-1 body weight. Hepatic 7-ethoxyresorufin-O-deethylase (EROD) activity was measured during the exposure and depuration periods, elucidating the time course pattern of CYP1A induction. Maximum induction (11-fold) of EROD activity was observed on day 2 after addition of BaP to the water. Tissue distribution of ³H-BaP was studied by liquid scintillation counting and whole body autoradiography. The concentration of ³H-BaP-derived radioactivity was highest in the bile at all sampling times. High levels of radiolabelled compound were also present in the gills, liver and the olfactory organ. There was an overall decrease in all tissues during the depuration period. The elimination of ³H-BaP-derived radioactivity from the gills, however, was slow compared with liver and blood (6.2 days vs 2.7 and 2.9 days, respectively).     

Production d'NH4 par la crevette Crangon crangon L. dans deux écosystémes côtiers. approche expérimentale et étude de l'influence du sédiment sur le taux d'excrétion

Estimation of the ammonia production of the shrimp C. crangon in two littoral ecosystems (oligotrophic sand and eutrophic mud) was determined in winter and summer conditions from laboratory observations in experimental microcosms. The ammonia excretion rate of C. crangon was not influenced by either the sediment type or the ammonia concentration of the overlying water; on the other hand, the mean excretion rate and the response to initial handling stress increased markedly as shrimp were deprived of soft substratum.

The daily ammonia production of C. crangon was 16 μmol NH₃ · g ⁻¹ wet wt · day ⁻¹ in winter and 40 μmol in summer. A gross production of 12 μmol NH₃ · m⁻² · day ⁻¹ and 300–700 μmol μ m⁻² · day⁻¹, respectively, could be expected in the two ecosystems studied. This would account for 5% (winter) and 2–4% (summer) of the total NH⁺₄ flux at the sediment-water interface. The contribution of the excretion of all macrofauna to the NH⁺₄ flux from the sediment is discussed.     

基于CdSe阳离子交换的玉米赤霉烯酮新型荧光免疫检测方法的建立及应用

作为镰刀属真菌的次级代谢产物,玉米赤霉烯酮(zearalenone,ZEN)具有强烈的生殖毒性和免疫毒性,严重威胁动物和人类健康。本研究通过采用羧基修饰的CdSe水溶性量子点(quantum dots,QDs)标记ZEN单克隆抗体,并基于CdSe阳离子交换信号增强原理,建立了ZEN新型荧光免疫检测方法(CdSe QDs-FLISA),检测下限(IC₁₀)和半数抑制率(IC₅₀)分别为0.006 ng/mL和0.17 ng/mL,检测区间(IC20–IC80)为0.01–0.45 ng/mL。与ZEN的结构类似物(α-zearalanol、zearalanone、α-zearalenol、β-zearalenol and β-zearalanol)交叉反应性依次为22.3%、13.1%、6.2%、1.6%和3.9%,与农产品中其他真菌毒素如黄曲霉毒素B₁(AFB₁)、赭曲霉毒素A(OTA)、呕吐毒素(DON)和伏马毒素B₁(FB₁)几乎不存在交叉反应。该方法...     

Simultaneous determination of urinary 1- and 2-naphthols, 3- and 9-phenanthrols, and 1-pyrenol in coke oven workers

A method was developed for simultaneous quantification of urinary 1- and 2-naphthols, 3- and 9-phenanthrols and 1-pyrenol using gas chromatography with mass spectrometry (GC-MS). This method was applied to urine samples from coke oven workers (n =28) and controls (n =22) from Northern China. Geometric mean levels of urinary 1-naphthol (58.8 μg l^-1), 2-naphthol (34.1 μg l^-1), 3-phenanthrol (7.35 μg l^-1), 9-phenanthrol (1.28 μg l^-1) and 1-pyrenol (25.4 μg l^-1) were significantly higher among coke oven workers than controls. All the substances tested were highest among top-of-oven workers, who had 15-fold higher 1-naphthol, eight-fold higher 2-naphthol and 20-fold higher 1-pyrenol levels compared with controls. Using multiple linear regression models, 72.5% of the variation in 1- and 2-naphthol and 82.8% of the variation in 1-pyrenol were explained by the concentration of naphthalene or pyrene in the urine, the work category and the smoking intensity. Cigarette consumption significantly contributed to levels of urinary 1-pyrenol and naphthols, particularly 2-naphthol. A negative relationship between work category and the ratio of naphthols/1-pyrenol was observed among smokers. Our results suggest that urinary naphthols and phenanthrols reflect polycyclic aromatic hydrocarbon (PAH) exposure as well as the widely used 1-pyrenol, and that interactions between cigarette smoking and PAH exposure result in different patterns of metabolism for individual PAHs.     

Effect of clomiphene on Ca movement in human prostate cancer cells

The effect of clomiphene, an ovulation-inducing agent, on cytosolic free Ca²⁺ levels ([Ca²⁺]_i) in populations of PC3 human prostate cancer cells was explored by using fura-2 as a Ca²⁺ indicator. Clomiphene at concentrations between 10-50 μM increased [Ca²⁺]_i in a concentration-dependent manner. The [Ca²⁺]_i signal was biphasic with an initial rise and a slow decay. Ca²⁺ removal inhibited the Ca²⁺ signal by 41%. Adding 3 mM Ca²⁺ increased [Ca²⁺]_i in cells pretreated with clomiphene in Ca²⁺-free medium, confirming that clomiphene induced Ca²⁺ entry. In Ca²⁺-free medium, pretreatment with 50 μM brefeldin A (to permeabilize the Golgi complex), 1 μM thapsigargin (to inhibit the endoplasmic reticulum Ca²⁺ pump), and 2 μM carbonylcyanide m-chlorophenylhydrazone (to uncouple mitochondria) inhibited 25% of 50 μM clomiphene-induced store Ca²⁺ release. Conversely, pretreatment with 50 μM clomiphene in Ca²⁺-free medium abolished the [Ca²⁺]_i increase induced by brefeldin A, thapsigargin or carbonylcyanide m-chlorophenylhydrazone. The 50 μM clomiphene-induced Ca²⁺release was unaltered by inhibiting phospholipase C with 2 μM 1-(6-((17β-3-methoxyestra-1,3,5(10)-trien-17-yl)amino)hexyl)-1H-pyrrole-2,5-dione (U73122). Trypan blue exclusion assay suggested that incubation with clomiphene (50 μM) for 2-15 min induced time-dependent decrease in cell viability by 10-50%. Collectively, the results suggest that clomiphene induced [Ca²⁺]_i increases in PC3 cells by releasing store Ca²⁺ from multiple stores in an phospholipase C-independent manner, and by activating Ca²⁺ influx; and clomiphene was of mild cytotoxicity.     

Fumonisin occurrence in corn from high- and low-risk areas for human esophageal cancer in China.

Forty-seven corn samples were collected in 1989 from Linxian and Shangqiu Counties in Henan Province, the high- and low-risk areas, respectively, for human esophageal cancer in the People's Republic of China. The samples were analyzed for fumonisin (fumonisin B1 [FB1] and FB2) contamination. Of the fumonisin-positive samples, the mean levels in Linxian corn were found to be 872 ng/g for FB1 and 448 ng/g for FB2, while the Shangqiu corns had 890 ng of FB1 and 330 ng of FB2 per g. The incidence of fumonisin contamination of Linxian corn (48%) was about two times higher than that of Shangqiu corn (25%), and the former corn samples were frequently cocontaminated with trichothecenes. Fusarium species isolated from corn from Linxian County produced FB1 at levels ranging from 1,280 to 11,300 micrograms/g.     

施氮量对不同藜麦品种幼苗生长的影响

通过盆栽试验,研究5个水平的施氮量(N₀,0 g·kg^-1;N₁,0.05 g·kg^-1;N₂,0.1 g·kg^-1;N₃,0.15 g·kg^-1;N₄,0.2 g·kg^-1)对8个不同藜麦品种幼苗生长的影响。结果表明: 1)不同施氮量处理下,藜麦品种GB22和OY的生物量最大,而品种B2的生物量最小。品种B2的花质量比最大,品种GB22的茎质量比最大,品种R1的根质量比最大,品种W23的叶质量比最大。2)施氮显著影响藜麦幼苗的生长。在较低施氮量(N₁、N₂)下,叶片最大净光合速率、植株生物量积累都比对照(N₀)明显增加;在较高施氮量(N₃、N₄)下,藜麦叶片光合速率出现降低趋势,生物量积累减少。品种和施氮量对植株生物量有显著的交互作用,表明不同藜麦品种对施氮量的响应不同。品种R1、MY11、GB22、OY的最佳施氮量为0.05 g·kg^-1,品种GB11、DB、B2的最佳施氮量为0.1 g·kg^-1,品种W23的最佳施氮量小于0.05 g·kg^-1。3)品种和施氮量之间的交互作用显著影响藜麦幼苗的生物量分配。在达到0.2 g·kg^-1施氮量前,随着施氮量增加,藜麦将更多的生物量分配到花和叶。4)不同品种和施氮量下,幼苗生物量与最大净光合速率、苗高、地径、比叶面积呈显著正相关。本研究可为不同藜麦品种的养分管理提供参考。     

The non-specific inhibition of enzymes by environmental pollutants: a study of a model system towards the development of electrochemical biosensor arrays

Previous research has shown that lactate dehydrogenase (LDH) was competitively inhibited by pentachlorophenol (PCP) and a modified assay produced a detection limit of 1 μM (270 μg l⁻¹). This work used spectrophotometric rate-determination but in order to move towards biosensor development the selected detection method was electrochemical. The linkage of LDH to lactate oxidase (LOD) provided the electroactive species, hydrogen peroxide. This could be monitored using a screen-printed carbon electrode (SPCE) incorporating the mediator, cobalt phthalocyanine, at a potential of +300 mV (vs. Ag/AgCl). A linked LDH/LOD system was optimised with respect to inhibition by PCP. It was found that the SPCE support material, PVC, acted to reduce inhibition, possibly by combining with PCP. A cellulose acetate membrane removed this effect. Inhibition of the system was greatest at enzyme activities of 5 U ml⁻¹ LDH and 0.8 U ml⁻¹ LOD in reactions containing 246 μM pyruvate and 7.5 μM NADPH. PCP detection limits were an EC₁₀ of 800 nM (213 μg l⁻¹) and a minimum inhibition detectable (MID) limit of 650 nM (173 μg l⁻¹). The inclusion of a third enzyme, glucose dehydrogenase (GDH), provided cofactor recycling to enable low concentrations of NADPH to be incorporated within the assay. NADPH was reduced from 7.5 to 2 μM. PCP detection limits were obtained for an assay containing 5 U ml⁻¹ LDH, 0.8 U ml⁻¹ LOD and 0.1 U ml⁻¹ GDH with 246 μM pyruvate, 400 mM glucose and 2 μM NADPH. The EC₁₀ limit was 150 nM (39.9 μg l⁻¹) and the MID was 100 nM (26.6 μg l⁻¹). The design of the inhibition assays discussed has significance as a model for other enzymes and moves forward the possibility of an electrochemical biosensor array for pollution monitoring.     

北亚热带地带性森林土壤温室气体通量对土地利用方式改变和降水减少的响应

弄清土地利用和降水变化对林地土壤主要温室气体(CO₂、CH₄和N₂O)排放通量变化的影响, 是准确评估森林土壤温室气体排放能力的重要基础。该研究以常绿落叶阔叶混交林原始林、桦木(Betula luminifera)次生林和马尾松(Pinus massoniana)人工林为对象, 采用静态箱-气相色谱法研究了3种土地利用方式(常绿落叶阔叶混交林原始林、桦木次生林和马尾松人工林)和降水减少处理状况下森林土壤CO₂、CH₄和N₂O通量排放特征, 并探讨了其环境驱动机制。研究结果表明: 原始林土壤CH₄吸收通量显著高于次生林和人工林, 次生林CH₄吸收通量显著高于人工林土壤。人工林土壤CO₂排放通量显著高于原始林和次生林土壤。次生林土壤N₂O排放通量高于原始林和人工林, 但三者间差异不显著。降水减半显著抑制了3种不同土地利用方式下林地土壤CH₄吸收通量; 降水减半处理对原始林和次生林土壤CO₂排放通量均具有显著的促进作用, 而对人工林土壤CO₂排放通量具有显著的抑制作用; 降水减半处理促进了原始林和人工林林地土壤N₂O排放而抑制了次生林林地土壤N₂O排放。原始林和次生林林地土壤CH₄吸收通量随土壤温度升高显著增加, CH₄吸收通量与土壤温度均呈显著相关关系; 原始林、次生林和人工林土壤CO₂和N₂O排放通量与土壤温度均呈显著正相关关系; 土壤湿度抑制了次生林和人工林土壤CH₄吸收通量, 其CH₄吸收通量随土壤湿度增加显著减少; 原始林土壤CO₂排放通量与土壤湿度呈显著正相关关系。自然状态下, 原始林土壤N₂O排放通量与土壤湿度呈显著正相关关系, 原始林和次生林土壤N₂O排放通量与硝态氮含量呈显著相关关系。研究结果表明全球气候变化(如降水变化)和土地利用方式的转变将对北亚热带森林林地土壤温室气体排放通量产生显著的影响。     

HPLC determination of fumonisin mycotoxins in maize: a comparative study of naphthalene-2,3-dicarboxaldehyde and o-phthaldialdehyde derivatization reagents for fluorescence and diode array detection

Fumonisins are mycotoxins produced by various species of Fusarium and occur naturally in contaminated maize and maize-based foods. Ingestion of fumonisins has considerable health implications for humans and animals. Since fumonisins lack a useful chromophore or fluorophore, their determination in maize is routinely achieved via HPLC with fluorescence detection (FLD) after precolumn derivatization. This study optimized naphthalene-2,3-dicarboxaldehyde (NDA) derivatization of fumonisins in naturally contaminated maize following strong anion exchange (SAX) solid phase extraction (SPE) clean-up and utilizing diode array detection (DAD) as a practical alternative simultaneously to FLD. The limit of detection (LOD) for fumonisin B(1) (FB(1)), fumonisin B(2) (FB(2)) and fumonisin B(3) (FB(3)) with FLD was 0.11 ng, 0.50 ng and 0.27 ng, respectively, and with DAD it was 13.8 ng, 12.5 ng and 6.6 ng, respectively injected on column. The coefficient of variation (CV, n = 6) for FB(1), FB(2) and FB(3) in a naturally contaminated samples obtained with FLD was 2.6%, 1.8% and 5.3%, respectively, compared to 6.0%, 3.4% and 9.5%, respectively, obtained with DAD. Subsequently the optimized NDA derivatization was compared to the widely used o-phthaldialdehyde (OPA) derivatization agent as well as alternative sample clean-up with immunoaffinity column (IAC) by analyzing naturally contaminated maize samples (n = 15) ranging in total fumonisin (TFB = FB(1)+FB(2)+FB(3)) levels from 106 to 6000 μg/kg. After immunoaffinity column clean-up of extracted samples, the recoveries of spiked maize samples for NDA-FLD of FB(1), FB(2) and FB(3) were 62%, 94% and 64%, respectively. NDA proved to be an effective derivatization reagent of fumonisin in naturally contaminated maize samples following IAC clean-up, except for DAD at TFB levels below 1000 μg/kg. In contrast NDA derivatization following SAX clean-up produced results comparable to OPA only for levels below 1000 μg/kg. Aside from the difference in detection limits, FLD and DAD produced comparable results irrespective of the clean-up method or the derivatization agent.     

Heterobimetallic chloro bridgedcomplexes of (η:η−C10H16)-ruthenium(IV) with palladium(II), platinum(II), rhodium(III), iridium(III), copper(I) and rhodium(I)

Metathesis of [(η³:η³−C₁₀H₁₆)Ru(Cl) (μ−Cl)]₂ (1) with [R₃P) (Cl)M(μ-Cl)]₂ (M = Pd, Pt), [Me₂NCH₂C₆H₄Pd(μ-Cl)]₂ and [(OC)₂Rh(μ-Cl)]₂ affords the heterobimetallic chloro bridged complexes (η³:η³-C₁₀H₁₆) (Cl)Ru(μ-Cl)₂M(PR₃)(Cl) (M = Pd, Pt), (η³:η³-C₁₀H₁₆) (Cl)Ru(μ-Cl)₂PdC₆H₄CH₂NMe₂ and (η³:η³-C₁₀H₁₆) (Cl)Ru(μ-Cl)₂Rh(CO)₂, respectively. Complex 1 reacts with [Cp^*M(Cl) (μ-Cl)]₂ (M = Rh, Ir), [p-cymene Ru(Cl) (μ-Cl]₂ and [(Cy₃P)Cu(μ-Cl)]₂ to give an equilibrium of the heterobimetallic complexes and of educts. The structures of (η³:η³-C₁₀H₁₆)Ru(μ-Cl)₂Pd(PR₃) (Cl) (R = Et, Bu) and of one diastereoisomer of (η³:η³-C₁₀H₁₆)Ru(μ-Cl)₂IrCp^*(Cl) were determined by X-ray diffraction.     

Greenhouse gas fluxes of typical northern subtropical forest soils: Impacts of land use change and reduced precipitation

Aims It is important to study the effects of land use change and reduced precipitation on greenhouse gas fluxes (CO₂, CH₄ and N₂O) of forest soils. Methods The fluxes of CO₂, CH₄ and N₂O and their responses to environmental factors of primary forest soil, secondary forest soil and artificial forest soil under a reduced precipitation regime were explored using the static chamber and gas chromatography methods during the period from January to December in 2014. Important findings Results indicate that CH₄ uptake of primary forest soil ((-44.43 ± 8.73) μg C·m^-2·h^-1) was significantly higher than that of the secondary forest soil ((-21.64 ± 4.86) μg C·m^-2·h^-1) and the artificial forest soil ((-10.52 ± 2.11) μg C·m^-2·h^-1). CH₄ uptake of the secondary forest soil ((-21.64 ± 4.86) μg C·m^-2·h^-1) was significantly higher than that of the artificial forest ((-10.52 ± 2.11) μg C·m^-2·h^-1). CO₂ emissions of the artificial forest soil ((106.53 ± 19.33) μg C·m^-2·h^-1) were significantly higher than that of the primary forest soil ((49.50 ± 8.16) μg C·m^-2·h^-1) and the secondary forest soil ((63.50 ± 5.35) μg C·m^-2·h^-1) (p < 0.01). N₂O emissions of the secondary forest soil ((1.91 ± 1.22) μg N·m^-2·h^-1) were higher than that of the primary forest soil ((1.40 ± 0.28) μg N·m^-2·h^-1) and the artificial forest soil ((1.01 ± 0.86) μg N·m^-2·h^-1). Reduced precipitation (-50%) had a significant inhibitory effect on CH₄ uptake of the artificial forest soil, while it enhanced CO₂ emissions of the primary forest soil and the secondary forest soil. Reduced precipitation had a significant inhibitory effect on CO₂ emissions of the artificial forest soil and N₂O emissions of the secondary forest (p < 0.01). Reduced precipitation promotes N₂O emissions of the primary forest soil and the artificial forest soil. CH₄ uptake of the primary forest and the secondary forest soil increased significantly with the increase of soil temperature under natural and reduced precipitation. CO₂ and N₂O emission fluxes of the primary forest soil, secondary forest soil and artificial forest soil were positively correlated with soil temperature (p < 0.05). Soil moisture inhibited CH₄ uptake of the secondary forest soil and the artificial forest soil (p < 0.05). CO₂ emissions of the primary forest soil were significantly positively correlated with soil moisture (p < 0.05). N₂O emissions of primary forest soil and secondary forest soil were significantly correlated with the nitrate nitrogen content (p < 0.05). It was implied that reduced precipitation and land use change would have significant effects on greenhouse gas emissions of subtropical forest soils.