Incidence and health risk assessment of hydrogen cyanide and multi-mycotoxins in Nigerian garri.

Garri is a granular, starchy food prepared by the fermentation of mashed cassava. Hydrogen cyanide (HCN) and mycotoxins are contaminants in certain foods at different points along the food value chain. The incidence and contamination levels of HCN and multi-mycotoxins in garri from five agroecological zones of Nigeria were determined using a spectrophotometric method and ultra-high-performance liquid chromatography-tandem mass spectroscopy (UHPLC-MS/MS), respectively. The health risk associated with the consumption of contaminated garri was assessed. The health risk assessment model was used to calculate the dietary exposure of humans to the mycotoxins in garri. This was done by estimating the daily intake (EDI), the percentage tolerable daily intake (%TDI), the annual hepatocellular carcinoma (HCC) cases attributable to exposure to aflatoxins (AFs) in garri, as well as the HCC risk. The average intake of garri was estimated at 0.303 kg/day for a Nigerian adult. The incidence of HCN was 98.3% (0.056-2.463 mg/kg), and fermentation reduced the HCN level in garri more than other processing steps. The twenty-one mycotoxins identified and quantified were all within maximum levels, as applicable to those that are regulated by the EU. The %TDI for the other mycotoxins, with the exception of AFs, showed no alarming health risk with garri consumption. Annual HCC cases resulting from AF in garri were estimated at 10-60 cases for HBsAg + ve individuals and 4-23 cases for HBsAg - ve individuals based on 8.1% hepatitis B virus (HBV) incidence. Results further revealed no interdependence between HCN levels and mycotoxin content. This work suggests an unlikely chance of acute toxicity from HCN and major mycotoxins from a garri-based diet in Nigeria. Hence, it is recommended that concerned regulatory bodies maintain the existing permissible limits for HCN in Garri.

Assessment of chemical asphyxia caused by toxic gases generated from rigid polyurethane foam (RPUF) fires.

Rigid polyurethane foam (RPUF) is widely used for thermal and sound insulation owing to their low thermal conductivity and light weight. However, they have serious disadvantages, including flammability and toxic gas generation, which can cause chemical asphyxia during a fire. Carbon monoxide (CO) and hydrogen cyanide (HCN) are representative toxic gases formed by incomplete combustion and HCN, in particular, is closely related to polyurethane product fires. In this study, the risk of inhalation of toxic gases such as CO, HCN and NO2 during RPUF fires was demonstrated convincingly through the analysis of carboxyhemoglobin (COHb), cyanide (CN-) and methemoglobin (MetHb) in the postmortem blood samples of 38 victims of RPUF fires. To better understand the toxic gas poisoning and chemical asphyxia, we classified all cases into two groups based on the extent of injuries and location where the victim was found. Mean concentrations of COHb and cyanide in group 1 without injuries were approximately two times higher than in group 2 with severe injuries, while concentrations of free MetHb showing possibility of NO2 inhalation were approximately six times lower than in group 2. Furthermore, we presumed concentrations of cyanide at the time of death and five cases showed the possibility of cyanide poisoning.

Hydrogen cyanide and carboxyhemoglobin assessment in an open space fire-related fatality.

Hydrogen cyanide (HCN) can be a major contributory factor in death from fire-related inhalation injury. Although carbon monoxide (CO) is considered the lethal agent of smoke in fires, its liability as a cause of death is sometimes debatable. The purpose of this report is to present the case of an 80-year-old man with locomotor disabilities who died due to an open space fire of vegetation debris and household waste in his yard. We evaluated here the concentrations of HCN and carboxyhemoglobin (COHb) and their contribution to the mechanism of death. In addition, the risk factors and the contributing effect of the factors that compose the complex toxic environment that develops in fires were discussed. COHb was determined by spectrophotometry as recommended by Katsumata et al. in 1982. HCN was determined with ninhydrin in postmortem blood samples after removal with 20% phosphoric acid and capture in a potassium carbonate solution. A toxic concentration of 1.3 µg ml-1 HCN and a lethal COHb level of 73.7% were determined in the blood samples. Although death was mainly attributed to CO poisoning and extremely severe burns in this open space burning case, the additive effect of HCN in the mechanism of death was also highlighted. The results suggested the possibility that the man's clothing may have played an important role in the production of HCN in this open space fire, as well as other types of garbage that were burned.

Plant tissue analysis as a tool for predicting fertiliser needs for low cyanogenic glucoside levels in cassava roots: An assessment of its possible use.

The use of plant tissue analysis as a tool for attaining low cyanogenic glucoside levels in cassava roots, has hardly been investigated. Just as the quality of crops is improved through the use of plant tissue analysis, the same can probably be done to consistently attain the lowest possible cyanogenic glucoside levels in cassava roots. High levels of cyanogenic glucosides in consumed fresh cassava roots or in their products have the potential of causing cyanide intoxication, hence the need to lower them. An experiment was thus conducted to assess the occurrence of meaningful relationships between plant nutritional status and cyanogenic glucoside production in cassava roots. Total hydrogen cyanide (HCN) levels in cassava roots were used to assess cyanogenic glucoside production. Using NPK fertiliser application to induce changes in plant nutritional status, the main objective of the study was investigated using the following sub-objectives; (1) to determine the effects of increased NPK fertiliser application on cassava root HCN levels; (2) and to show the occurrence of relationships between changes in nutrient levels in plant 'indicator tissue' and HCN levels in cassava roots. The study was a field experiment laid out as a split-plot in a randomized complete block design with three replicates. It was repeated in two consecutive years, with soil nutrient deficiencies only being corrected in the second year. The varieties Salanga, Kalinda, Supa and Kiroba were used in the experiment, while the NPK fertiliser treatments included; a control with no fertiliser applied; a moderate NPK treatment (50 kg N + 10 kg P + 50 kg K /ha); and a high NPK treatment (100 kg N + 25 kg P + 100 kg K /ha). A potassium only treatment (50 kg K/ha) was also included, but mainly for comparison. The root HCN levels of Salanga, Kalinda and Kiroba were significantly influenced by NPK fertiliser application in at least one of the two field experiments, while those of Supa remained uninfluenced. Changes in plant nutritional status in response to fertiliser application were thus shown to influence cyanogenic glucoside production. The results of the multiple linear regression analysis for the first field experiment, generally showed that the root HCN levels of some cassava varieties could have been 'reduced' by decreasing concentrations of nitrogen, potassium and magnesium in plants, or by improving plant calcium concentrations along with NPK fertiliser application. However, in the second field experiment (with corrected soil nutrient deficiencies) the regression analysis generally showed that the root HCN levels of some cassava varieties could have been 'reduced' by improving either one or a combination of the nutrients phosphorous, zinc and potassium in plants along with NPK fertiliser application. Although the results obtained in the two experiments had been contradicting due to slight differences in how they were conducted, the study had nonetheless demonstrated the occurrence of meaningful relationships between plant nutritional status and cyanogenic glucoside production; confirming the possible use of plant tissue analysis in predicting fertiliser needs for the consistent attainment of low cyanogenic glucosides in cassava roots.

Antinutritional factors and hypocholesterolemic effect of wild apricot kernel (Prunus armeniaca L.) as affected by detoxification.

The present investigation was aimed to study the effect of detoxification on the nutrients and antinutrients of wild apricot kernel followed by its hypocholesterolemic effect in male Wistar albino rats. The results revealed a non-significant (p > 0.05) effect of detoxification on the proximate composition except total carbohydrates and protein content. However, detoxification led to a significant (p < 0.05) decrease in l-ascorbic acid (76.82%), ß-carotene (25.90%), dietary fiber constituents (10.51-28.92%), minerals (4.76-31.08%) and antinutritional factors (23.92-77.05%) (phenolics, tannins, trypsin inhibitor activity, saponins, phytic acid, alkaloids, flavonoids, oxalates) along with the complete removal (100%) of bitter and potentially toxic hydrocyanic acid (HCN). The quality parameters of kernel oil indicated no adverse effects of detoxification on free fatty acids, lipase activity, acid value and peroxide value, which remained well below the maximum permissible limit. Blood lipid profile demonstrated that the detoxified apricot kernel group exhibited significantly (p < 0.05) increased levels of HDL-cholesterol (48.79%) and triglycerides (15.09%), and decreased levels of total blood cholesterol (6.99%), LDL-C (22.95%) and VLDL-C (7.90%) compared to that of the raw (untreated) kernel group. Overall, it can be concluded that wild apricot kernel flour could be detoxified efficiently by employing a simple, safe, domestic and cost-effective method, which further has the potential for formulating protein supplements and value-added food products.

Risk assessment in combustion toxicology: Should carbon dioxide be recognized as a modifier of toxicity or separate toxicological entity?

To characterize the accumulated hazards associated with the inhalation of gases typical of combustion products, a time-integrated value known as the fractional effective dose (FED) is used. This FED is maintained by the International Organization for Standardization (ISO) and made publicly available as the Standard ISO 13571. The current FED calculation related to asphyxiant gases is based on non-human primate data to estimate the 50% probability of humans to be incapacitated or not being able to execute any escape paradigm from fires. The objective of this paper was to compare two to calculate FEDs of the most common mixture of asphyxiant fire gases CO, HCN, and CO2. The first was based on the current ISO 13571 (draft) standard, the alternative second method applied the conceptual principles established for the derivation of Acute Emergency Response Planning Guideline values. The alternative approach applied one third of the non-lethal threshold concentration (LC01) as the most suitable and robust Point of Departure (POD) to estimate the threshold characterizing 'impairment of escape' in the absence of post-exposure mortality. The hyperventilation correction factor for CO2 of ISO 13571 was replaced by a separate term that accounts for the inherent acute toxicity of CO2. This analysis supports the conclusion that the current ISO 13571 standard misjudges the impact of the acute toxicity elicited by concentrations of CO2 exceeding ≈6%. While underestimating the hazards attributable to CO2, the hyperventilation adjustment factor suggested by this standard is biased to markedly overestimate the hazards assigned to CO and HCN in fire effluents.

Case Files of the University of Massachusetts Toxicology Fellowship: Does This Smoke Inhalation Victim Require Treatment with Cyanide Antidote?

Cyanide toxicity is common after significant smoke inhalation. Two cases are presented that provide framework for the discussion of epidemiology, pathogenesis, presenting signs and symptoms, and treatment options of inhalational cyanide poisoning. An evidence-based algorithm is proposed that utilizes point-of-care testing to help physicians identify patients who benefit most from antidotal therapy.

Assessment of carboxyhemoglobin, hydrogen cyanide and methemoglobin in fire victims: a novel approach.

To establish the cause of death, carboxyhemoglobin (COHb), total hemoglobin (tHb), methemoglobin (MetHb), and hydrogen cyanide (HCN) were quantified in the blood of fire victims. We analyzed 32 out of 33 blood samples from forensic autopsy cases in a disastrous polyurethane mattress fire, which caused the deaths of 33 inmates at a prison in Argentina in 2006. The cadaveric blood samples were collected by femoral vein puncture. These samples were analyzed using the IL80 CO-oximeter system for tHb, MetHb, and COHb levels and by microdiffusion for HCN and COHb levels. Blood alcohol (ethanol) and drugs were examined by headspace gas chromatography-flame ionization detection (HS-GC-FID) and GC-mass spectrometry (MS), respectively. Polyurethane mattress samples were analyzed according to the California 117 protocol. The saturation of COHb ranged from 10% to 43%, tHb from 2% to 19.7%, MetHb from 0.10% to 35.7%, and HCN from 0.24 to 15mg/L. These HCN values are higher than the lethal levels reported in the literature. Other toxic components routinely measured (ethanol, methanol, aldehydes, and other volatile compounds) gave negative results in the 32 cases. Neither drugs of abuse nor psychotropic drugs were detected. The results indicate that death in the 32 fire victims was probably caused in part by HCN, generated during the extensive polyurethane decomposition stimulated by a rapid increase in temperature. We also considered the influence of oxygen depletion and the formation of other volatile compounds such as NOx in this disaster, as well as pathological evidence demonstrating that heat was not the cause of death in all victims. Furthermore, statistical analysis showed that the percentage values of COHb and MetHb in the blood were not independent variables, with χ(2)=11.12 (theoretical χ(2)=4.09, degrees of freedom=12, and α=0.05). However, no correlation was found between HCN and MetHb in the blood of the victims. This is the first report to assess the relationship between COHb and MetHb in forensic blood samples. We further discuss other factors that could lead to a lethal atmosphere generated by the fire and compare the data from this disaster with that of other published fire episodes.

[Assessment of exposure to hydrogen cyanide in fire fatalities in the aspects of endogenous hydrogen cyanide production as a result of putrefaction processes in the deceased]. / Ocena ekspozycji na cyjanowodór u smiertelnych ofiar pozarów w aspekcie powstawania w zwlokach endogennego cyjanowodoru w procesach gnilno-rozkladowych.

On account of endogenous hydrogen cyanide (HCN) production in the deceased, it is not easy to assess exposure to HCN in people who died in fire involving closed rooms (flats, garages, cellars, etc). In the paper, the authors present the results of blood determinations of hydrogen cyanide in fatalities of explosions and fires occurring in coal-mines, as well as fires in closed rooms. It has been demonstrated that the time of exposure to a high temperature and the temperature itself hamper autolysis processes that lead to production of endogenous HCN in fire fatalities.

Exposure assessment through realistic laboratory simulation of a soccer stadium fire.

On Sunday April 13, 2008 a fire broke out on a grandstand in the Euroborg soccer stadium in Groningen The Netherlands. The polyamide chairs on the grandstand were set on fire and supporters were exposed to the emitted smoke which induced mild health effects. The Dutch government was concerned about potential health risks that such fires could have to exposed fans. Especially the exposure to toxic fumes was considered a risk because prior research has proven that large amounts of chemical compounds are emitted during the burning of chemical substances such as polyamide. Among these emitted compounds are HCN, CO, NO(x), NH(3) and volatile organic compounds. To study if supporters were exposed to hazardous chemical compounds we designed a laboratory controlled replica of a part of the grandstand of the Euroborg stadium to perform fire-experiments. This simulation of the fire under controlled circumstances proved that a wide variety of chemicals were emitted. Especially the emission of CO and NO(x) were high, but also the emission of formaldehyde might be toxicologically relevant. The emission of HCN and NH(3) were less than expected. Exposure assessment suggests that the exposure to NO(x) is the main health risk for the supporters that were present at the Euroborg fire.

Rovibrational spectra for the HCCCN*HCN and HCN*HCCCN binary complexes in 4He droplets.

Rovibrational spectra are measured for the HCCCN*HCN and HCN*HCCCN binary complexes in helium droplets at low temperature. Though no Q-branch is observed in the infrared spectrum of the linear HCN*HCCCN dimer, which is consistent with previous experimental results obtained for other linear molecules, a prominent Q-branch is found in the corresponding infrared spectrum of the HCCCN*HCN complex. This Q-branch, which is reminiscent of the spectrum of a parallel band of a prolate symmetric top, implies that some component of the total angular momentum is parallel to the molecular axis. The appearance of this particular spectroscopic feature is analyzed here in terms of a nonsuperfluid helium density induced by the molecular interactions. Finite temperature path integral Monte Carlo simulations are performed using potential energy surfaces calculated with second-order Möller-Plesset perturbation theory, to investigate the structural and superfluid properties of both HCCCN*HCN(4He)N and HCN*HCCCN(4He)N clusters with N < or = 200. Explicit calculation of local and global nonsuperfluid densities demonstrates that this difference in the rovibrational spectra of the HCCCN*HCN and HCN*HCCCN binary complexes in helium can be accounted for by local differences in the superfluid response to rotations about the molecular axis, i.e., different parallel nonsuperfluid densities. The parallel and perpendicular nonsuperfluid densities are found to be correlated with the locations and strengths of extrema in the dimer interaction potentials with helium, differences between which derive from the variable extent of polarization of the CN bond in cyanoacetylene and the hydrogen-bonded CH unit in the two isomers. Calculation of the corresponding helium moments of inertia and effective rotational constants of the binary complexes yields overall good agreement with the experimental values.

[Attempt to estimate risks of fatal poisoning on the basis of HCN and HbCO concentrations in blood of fire victims]. / Próba oceny ryzyka smiertelnego zatrucia na podstawie ksztaltowania sie stezenia cyjanowodoru i karboksyhemoglobiny we krwi ofiar pozarów.

Using the results of HCN and HbCO concentrations in the blood of 174 deceased found in different burning spaces and 35 people with symptoms of poisoning evacuated from the scene of a fire and then admitted to hospital. The correlation between blood concentration of both these xenobiotics and death or chance of survival in a fire was estimated by statistical analysis. An attempt was made to define a value of so-called "cut-off" points for HbCO and HCN by independence test chi 2 with Yates's correction. Point and interval estimations (95% Comfield's confidence interval) were used for the odds ratio (OR). The research showed that there was a strict statistical correlation between the chance of survival and death risks dependent on blood concentrations of HCN and HbCO in all the groups examined.

Nutrient content of young cassava leaves and assessment of their acceptance as a green vegetable in Nigeria.

Cassava (Manihot esculenta Crantz) leaves contained a high level of crude protein (29.3-32.4% dry weight) compared to a conventional vegetable, Amaranthus (19.6%). Ash was 4.6-6.4% in cassava leaf samples but 13.1% dry weight in Amaranthus. Dietary fibre was very high in all samples (26.9-39% dry weight) while HCN-potential was low (5.1-12.6 mg/100 g dry weight). Tannin was the highest in IITA red cassava leaves (29.7 mg/g) and the lowest in Amaranthus vegetable. In vitro digestibility was very low in oven dried samples (15.6-22.7%). Blanching increased protein content (except Amaranthus) and in vitro protein digestibility but decreased ash, minerals, dietary fibre and tannin, while HCN-potential was unchanged. Grinding reduced both HCN-potential and tannin by 84 and 71% respectively while oven drying only reduced the HCN content marginally. Preference studies showed that the highest percentage of respondents (25.3%) preferred Amaranthus vegetable, followed by Celosia (17.5%), Talinum (12.4%), garden egg (11.5%), with cassava leaves as the least (0.5%). Organoleptic evaluation rated cassava leaf soup inferior to Amaranthus in terms of appearance, colour and texture but equal in terms of taste and flavour and overall acceptability.

The evolution of toxic effluents in fires and the assessment of toxic hazard.

Toxic hazard in fire depends upon three factors: the fire growth curve (mass loss rate of materials, kg/min) and volume dispersal (kg/m3), the yields of toxic products (e.g. kg CO/kg fuel burned) and the toxic potency of the products (exposure dose needed to cause toxic effects, e.g. lethal dose of CO in ppm.min). The first and second sets of data are obtainable from large-scale tests or small-scale tests and mathematical modelling, the third and some information on the second are derived from toxicity studies of combustion products in small-scale tests or of individual fire gases. Small-scale toxicity test data on materials expressed as lethal mass loss exposure doses (LCt50 g min m-3) can be used in Fractional Effective Dose (FED) hazard assessments, providing the decomposition conditions of the test reproduce those in the fire being examined; principally either non-flaming oxidative, early well-ventilated flaming, or vitiated post-flashover. Although bioassays are needed for a full toxicity assessment, it is now possible to predict the toxic potency of materials to some extent from analytical data alone. The suitability of the small-scale test decomposition conditions are determined in terms of non-flaming or flaming behaviour, temperature (or radiant flux), CO2/CO ratio and oxygen concentration. Existing small-scale test methods provide reasonable models for materials under non-flaming oxidative and early flaming conditions, although the data base for the latter is poor. Only the DIN 53436 method is able to model vitiated post-flashover decomposition conditions, but data for this condition are almost non-existent.

Air sampling in the assessment of continuous exposures to acutely-toxic chemicals. Part I--Strategy.

This paper describes the conceptual basis for assessing the hazard of continuous exposures to acutely toxic chemicals. It is stressed that the variability of workers' short-term exposures to airborne chemicals must be considered in establishing strategic criteria which define an acceptable (or unacceptable) environment. The argument is developed that the traditional strategy of an absolute ceiling limit is unworkable since any set of exposures can be declared out of compliance if a sufficiently large number of samples is collected. It is proposed that acute-exposure limits be defined instead as air concentrations that can be exceeded by an explicit fraction of the population of exposures. An "exceedance" rate of 5% is suggested provided that exposure limits incorporate appropriate safety factors which are relatively large for potent acute toxins and small for irritants. The implications of this strategy are analyzed with some existing ceiling limits proposed by NIOSH.