Evaluation of Arsenic Leaching Potential in Gold Mine Tailings Amended with Peat and Mine Drainage Treatment Sludge.

Peat and mine drainage treatment sludge can be valorized as amendments on mine sites to stabilize gold mine tailings and reduce the potential leaching of contaminants in pore water. However, the influence of organic amendments on the mobility of metalloids and/or metals in the tailings must be validated, as the leached contaminants may vary according to their type, nature, and origin. The objective of the present study was to evaluate over time the effect of peat- and/or Fe-rich sludge amendments on the mobility of As and metallic cations in the drainage water of tailings potentially producing contaminated neutral drainage. Ten duplicated weathering cell experiments containing tailings alone or amended with peat and/or Fe-rich sludge (5-10% dry weight) were performed and monitored for 112 d. The results showed that as low as 5% peat amendment would promote As mobility in tailings' pore water, with As concentrations exceeding Quebec discharge criteria (>0.2 mg L). In addition, As(III), the most mobile and toxic form, was predominant with 10% peat, whereas organic species were negligible in all cells. The use of peat alone as organic amendment for the stabilization of tailing contaminants could increase the risk of generating As-rich contaminated neutral drainage. Conversely, the mix of only 5% Fe-rich sludge with or without peat decreased As concentrations in leachates by 65 to 80%. Further studies on the use of "peat" or "peat + Fe-rich sludge" as cover or amendment should be conducted with a focus on Fe/As and Ca/As ratios.

The views of parents who experience intergenerational poverty on parenting and play: a qualitative analysis.

BACKGROUND: There is minimal literature on how parents experiencing intergenerational poverty view their role as parents and the value they place on children's play. The objective of this study was to examine how these parents view their parenting role and their beliefs about children's play. METHODS: Thirteen mothers of preschool-aged children who experienced intergenerational poverty were recruited to the study. Semi-structured interviews were conducted and were analysed using interpretive phenomenological analysis. RESULTS: Parents described their role as guiding their children to become 'good' people, to teach them skills and provide a routine within the home. There were two disconnections in the data including the view that whilst parenting was hard and lonely, it was also a private matter and participants preferred not to seek support. A second disconnection was in terms of their beliefs about play. Parents believed that whilst play was valuable to their child's development, it was not their role to play with children. However, if parents did play with their child, they noticed positive changes in their child's behaviour. CONCLUSION: The views of parents who experienced intergenerational poverty were similar to other reported findings in parenting studies. However, the current sample differed on not seeking help for support as well as not seeing their role as playing with their children, even though occasions of joining their child in play were associated with a positive change in their relationship with their child. This has implications for communicating about parenting issues with parents who have experienced intergenerational poverty.

[Analytical, toxicological and forensic aspects of drug-facilitated crimes: 10 years of experience]. / Aspects analytique, toxicologique, judiciaire de la soumission chimique : dix ans d'expérience.

Although being a relatively old phenomenon, drug-facilitated crime has been well described over the past 20 years as being the administration without the knowledge of the victim of a psychoactive substance in criminal purposes (rape, robbery, theft, money extortion, even murder). Drug-facilitated crime involves also mistreatment of older people or children treated by their parents in order to obtain sedation. Drug-facilitated crimes are often difficult to solve mainly due to analytical issues. Since 10 years, we developed and improved specific methods using LC-MS/MS (benzodiazepines, neuroleptics) and GC-MS/MS (GHB, cannabis) to detect the drugs involved in such crimes. After the intake of a low dosage of a particular drug, those methods allow to detect the analyte of interest up to 3-5 days in blood, 10-15 days in urine, and more than 1 year in hair. In drug-facilitated crime cases, blood and urine are frequently collected too late, more than 12 h after the drug intake and in some cases with a delay greater than 48 h after the event. Thus, the most used molecules are undetectable by the techniques classically used in a laboratory of biology. Moreover, a "good" compound that can be used to commit a drug-facilitated crime usually possesses a short elimination half-life and amnesic properties, so that the victim is less able to accurately recall the circumstances under which the offence occurred. The recent progress in analytical toxicology, particularly for laboratories working in the field of forensic toxicology, permits to elucidate many cases of drug-facilitated crimes. Heaven to the introduction of the sequential analysis of hair and the use of sophisticated analytical techniques such as tandem mass-spectrometry for the toxicologist to bring the scientific proof to the applicant authorities in the description of the criminal act and to confuse the offender. The author presents the results of 583 presumed cases of drug-facilitated crimes analyzed by his laboratory specialized in forensic toxicology. One hundred and seventy of those cases were confirmed by the analyses of the blood and/or the urine and/or hair, in which molecules frequently encountered, were identified.

[Drug-facilitated crime and sexual abuse: a pediatric observation]. / Soumission chimique et agression sexuelle chez l'enfant: à propos d'une observation.

Drug-facilitated crime in sexual assault situations remains insufficiently recognized by physicians. In the possible context of an assault and in front of recent neuropsychicological disturbances in a child, such an issue has to be considered. The quality of sampling, the use of ultra-sensitive and specific toxicologic methods and a clinical-biological collaboration allow to recognize this form of delinquency whose consequences are both medical and legal.

Use of drugs of abuse in less than 30-year-old drivers killed in a road crash in France: a spectacular increase for cannabis, cocaine and amphetamines.

A collaborative study was conducted in France in order to determine the prevalence of cannabinoids, opiates, cocaine metabolites and amphetamines in blood samples from drivers killed in road accidents in 2003 and 2004 and to compare these values with those of a previous study performed during the period 2000-2001 involving 900 drivers. Blood samples were provided from 2003 under 30-year-old drivers, killed in a traffic accident. Drugs of abuse were determined by gas chromatography-mass spectrometry using the same analytical procedures in all the 12 laboratories. The most frequently observed compounds were by far cannabinoids, that tested positive in 39.6% of the total number of samples. Delta9 tetrahydrocannabinol (THC), the most active of the principle constituents in marijuana (cannabis sativa), was detected in the blood of 28.9% drivers and was the single drug of abuse in 80.2% of the positive cases. It was associated with amphetamines in 7.4% and with opiates and cocaine in 1.9 and 4.8%, respectively. Amphetamines were present in 3.1% of the total number of samples, cocaine metabolites in 3.0% and opiates in 3.5%. When comparing these results with those of a previous study performed 3 years before, a significant increase is observed for THC (28.9% versus 16.9%), cocaine metabolites (3.0% versus 0.2%) and amphetamines (3.1% versus 1.4%). This study demonstrates the critical necessity of implementing in France as soon as possible systematical roadside testing for drugs of abuse.

Identification of alprazolam in hair in two cases of drug-facilitated incidents.

The use of a drug to modify a person's behaviour for criminal gain is not a recent phenomenon. However, the recent increase in reports of drug-facilitated crimes (sexual assault, robbery) has caused alarm by the general public. Among the drugs that can be used, alprazolam (Xanax), an anxiolytic benzodiazepine, has been seldom observed. To document two cases involving this drug, we have developed an approach based on hair testing by LC-MS/MS. After pH 8.4 buffer incubation and extraction with methylene chloride/diethyl ether (80/20, v/v), hair extracts were separated on a XTerra MS C18 column using a gradient of acetonitrile and formate buffer. Alprazolam and diazepam-d5, used as internal standard, were detected by electrospray tandem mass spectrometry. In the first criminal case, alprazolam tested positive in two consecutive 2 cm hair segments at 4.9 and 2.4 pg/mg, from a 12-year-old girl, assaulted by her father who had sedated her three or four times. In the other case, alprazolam was detected in four consecutive 1cm hair segments at 3.1-0.4 pg/mg, obtained from an adolescent who had been forced to prostitute herself.

[Alcohol, pharmaceuticals, illicit drugs and driving]. / Alcool, médicaments, stupéfiants au volant.

A great number of clinical, epidemiological, pharmacological and toxicological data on the influence of psychotropics on driving are available. These psychotropics include psycholeptics like ethanol, opioids, psychoanaleptics like cocaine, amphetamines and congeners, psychodysleptics like cannabis, LSD and magic mushrooms. General epidemiology and specific epidemiology for Luxembourg will be outlined. Practical aspects of roadside testing, forensic aspects as well as the place of hair testing in drugs and road safety issues will be discussed.

Screening procedure for eight quaternary nitrogen muscle relaxants in blood by high-performance liquid chromatography-electrospray ionization mass spectrometry.

A screening procedure was developed for the identification and the quantification of eight quaternary nitrogen muscle relaxants, including d-tubocurarine, alcuronium, pancuronium, vecuronium, atracurium, mivacurium, rocuronium and mebezonium, in blood samples. The procedure involves ion-pair extraction with methylene chloride at pH 5.4, reversed-phase HPLC separation and electrospray ionization mass spectrometry detection. The procedure was validated in terms of linearity (0.9295 for all the target compounds at 0.1 mg/l). The screening test was found satisfactory and applied in two fatal deaths. In the first case, toxicological investigations on biological fluids collected during the autopsy revealed the presence of vecuronium (1.2 and 0.6 mg/l in blood and urine, respectively) and its desacetylated metabolite, 3-hydroxy-vecuronium (4.4 and 0.7 mg vecuronium equivalent/l in blood and urine, respectively). In the second forensic case, blood analysis showed high levels of mebezonium (6.5 mg/l). The developed procedure was found suitable for forensic investigations.

Plasma lipids in Turkish children: impact of puberty, socioeconomic status, and nutrition on plasma cholesterol and HDL.

In Turkish adults, HDL cholesterol (HDL-C) levels are 10-15 mg/dl lower than those of adults in western Europe and the United States. In this study, we determined whether HDL-C levels in Turks are low from birth to adulthood and assessed the effect of socioeconomic status (SES) on plasma lipids and lipoproteins. Analyses of cord blood from 105 Turkish newborns showed low levels of plasma cholesterol ( approximately 60 mg/dl) and HDL-C (approximately 30 mg/dl), consistent with results from other Western ethnic groups. Prepubescent 8- to 10-year-old Turkish boys and girls of upper (n = 82) and lower (n = 143) SES had high HDL-C levels (50-60 mg/dl) similar to those of western European children. However, the cholesterol (154-158 mg/dl) and HDL-C (55-58 mg/dl) levels of upper SES children were approximately 25 and approximately 12 mg/dl higher, respectively, than those of lower SES children. Height, weight, skinfold thickness, and estimated body fat were greater in the upper SES children and appeared to reflect dietary differences. Upper SES children consumed more total fat (approximately 35% vs. 25% of total calories), including more saturated fat of animal origin, and less carbohydrate (approximately 50% vs. 62% of total calories), consistent with their elevated plasma cholesterol levels. Carbohydrate intake correlated inversely with the HDL-C level. The HDL-C levels in the prepubescent children, especially those of higher SES, who consumed diets more like western Europeans, decreased markedly to adult levels, with males exhibiting a approximately 20 mg/dl decrease (from 58 to 37 mg/dl) and females a approximately 13 mg/dl decrease (from 55 to 42 mg/dl). SES did not affect HDL-C levels in adults. The profound decrease may reflect alterations in androgen/estrogen balance in Turks at puberty and a modulation of hepatic lipase affecting HDL-C levels.

[Human main plant poisoning: revue of the literature]. / Intoxications humaines par les végétaux supérieurs: revue de la littérature.

The authors have reviewed the main toxic plants responsible for human deaths throughout the world. Forty plants (genera or species) were listed in order to establish an inventory of the botany of the plant, its use, the active molecules that could be identified, the already published analytical methods and the reported human fatal cases.

LC-EI-MS determination of veratridine and cevadine in two fatal cases of Veratrum album poisoning.

We report two fatal poisonings due to the ingestion of plant material. The two deceased were discovered in the water of a mountain lake about one month after the postmortem immersion of the corpses. Macroscopic examination of the stomachs revealed the presence of a very large number of small blackish granules, which were later identified as seeds of a Veratrum species. Veratridine and cevadine were identified and quantitated by high-performance liquid chromatography-electrospray ionization-mass spectrometry. Measured blood concentrations were 0.17 and 0.40 ng/mL for veratridine and 0.32 and 0.48 ng/mL for cevadine. The absence of other toxic substance led to the assumption that this massive ingestion was the cause of death, although the circumstances surrounding intake remained unknown.

[Urinary nandrolone metabolites in antidoping control]. / A propos des métabolites de la Nandrolone dans les contrôles urinaires antidopage.

The French National Laboratory of the International Olympic Committee (IOC) has detected norandrosterone (NA) and noretiocholanolone (NE) in urine samples from several sportsmen. These two substances are known to be urinary metabolites after nandrolone intake. In such cases, the NA level is always higher than the Ne level. However, in the urine samples of sportsmen tested positive, the NE concentrations were systematically higher than the NA levels. We therefore searched for other steroid precursors (commercially available capsules or tablets of dehydroepiandrosterone, 4-androstenediol, 5-androstenediol, 4-androstenedione, 19-norandrostenediol and 19-norandrostenedione, also illegally used in France) which could lead to an excretion of NA and NE and to an inverted ratio of these metabolites.

Analysis of corticosteroids in hair by liquid chromatography-electrospray ionization mass spectrometry.

The present study describes a confirmatory method for the quantitative determination in hair of the most common corticosteroids illegaly used as doping agents by athletes. Corticosteroids are extracted from 50 mg of powdered hairs by methanolic extraction follows by a solid-phase extraction on C18 cartridge. After extraction, the dried residue is reconstituted with 50 microl acetonitrile and injected in a liquid chromatograph. Liquid chromatography separation is performed on a reversed-phase C18 column with a binary gradient of formiate buffer pH 3-acetonitrile as mobile phase. Detection is performed with an electrospray ionization mass spectrometer in negative ion and selected-ion monitoring mode. The limits of sensitivity achieved is 0.1 ng/mg in hair. Application to hair sample collected during an antidoping control and comparison to results obtain on urines, collected on the same athletes at the same time, shows the interest and the complementarity of both matrices. Hair analysis could allow the detection of corticosteroids on a large period preceding the control, and the detection of natural corticosteroids administered as pro-drug, like hydrocortisone acetate.

Fatal aluminum phosphide poisoning.

A 39-year-old man committed suicide by ingestion of aluminum phosphide, a potent mole pesticide, which was available at the victim's workplace. The judicial authority ordered an autopsy, which ruled out any other cause of death. The victim was discovered 10 days after the ingestion of the pesticide. When aluminum phosphide comes into contact with humidity, it releases large quantities of hydrogen phosphine (PH3), a very toxic gas. Macroscopic examination during the autopsy revealed a very important asphyxia syndrome with major visceral congestion. Blood, urine, liver, kidney, adrenal, and heart samples were analyzed. Phosphine gas was absent in the blood and urine but present in the brain (94 mL/g), the liver (24 mL/g), and the kidneys (41 mL/g). High levels of phosphorus were found in the blood (76.3 mg/L) and liver (8.22 mg/g). Aluminum concentrations were very high in the blood (1.54 mg/L), brain (36 microg/g), and liver (75 microg/g) compared to the usual published values. Microscopic examination revealed congestion of all the organs studied and obvious asphyxia lesions in the pulmonary parenchyma. All these results confirmed a diagnosis of poisoning by aluminum phosphide. This report points out that this type of poisoning is rare and that hydrogen phosphine is very toxic. The phosphorus and aluminum concentrations observed and their distribution in the different viscera are discussed in relation to data in the literature.

Compared interest between hair analysis and urinalysis in doping controls. Results for amphetamines, corticosteroids and anabolic steroids in racing cyclists.

In France during a famous bicycle race, the newspapers documented the degree in which doping seemed to be supervised in some teams by managers and doctors. Use of anabolic steroids and other substances was officially banned in the mid-seventies by sports authorities. This policy has been enforced through urine testing before competition. It is well known, however, that a latency period is all that is necessary to defeat these tests. Nevertheless, hair analysis could be a promising tool when testing for periods that are not accessible to urinalysis any more. We have developed different sensitive methods for testing hair for amphetamines, anabolic steroids and their esters and corticosteroids. For amphetamines, 50 mg of hair were digested with 1 M NaOH, extracted with ethyl acetate, derivatized with TFA and analyzed by gas chromatography positive chemical-ionization mass spectrometry. For corticosteroids, 50 mg of powdered hair were treated with methanol in an ultrasonic bath and subsequently purified using a C18 solid phase extraction column. Analysis was realized by high performance liquid chromatography coupled to electrospray-ionization tandem mass spectrometry. For anabolic steroids and their esters, 100 mg of powdered hair were treated with methanol in an ultrasonic bath for extraction of esters, then alkaline digested with 1 M NaOH for an optimum recovery of other drugs. The two liquid preparations were subsequently extracted with ethyl acetate, pooled, then finally highly purified using a twin solid phase extraction on aminopropyl and silica cartridges. Residue was derivatized with MSTFA prior to injection. Analysis was conducted by gas chromatography coupled to a triple quadrupole mass spectrometer. Thirty cyclists were sampled and tested both in hair and in urine. Amphetamine was detected 10 times in hair (out of 19 analyses) compared to 6 times in urine (out of 30 analyses). Corticosteroids were detected 5 times in hair (methylprednisolone 1 case, triamcinolone acetonide 3 cases and hydrocortisone acetate 1 case) in hair (out of 12 analyses) compared to 12 times (triamcinolone acetonide 10 cases and betamethasone 2 cases) in urine (out of 30 analyses). Anabolic steroids were detected twice (nandrolone 1 case, and testosterone undecanoate 1 case) in hair (out of 25 analyses) compared to none in urine (out of 30 analyses).

The hair analysis proficiency testing program of the French Society of Analytical Toxicology.

In an effort to improve laboratories performing hair analysis in forensic cases, the French Society of Analytical Toxicology (S.F.T.A.) has implemented a proficiency testing program since 1992. Actually about 10 laboratories are participating. Each survey is dedicated to one analyte or one pharmacological class: opiates (6-monoacetylmorphine, morphine and codeine), cocaine and benzoylecgonine, tetrahydrocannabinol, buprenorphine and norbuprenorphine, beta-blockers (metoprolol, atenolol), beta 2-agonists (salbutamol, clenbuterol). Animal hair was tested for clenbuterol. Prior to sending, hair samples were reduced to a powdered form, well mixed to ensure homogeneity, and then tested by GC/MS or HPLC/MS. Results confirm those obtained in a preliminary study on opiates and cocaine analysis in hair: a common analytical procedure has to be used by all the participants, including hydrolysis of hair. It is essential to work on authentic drug-positive hair samples and not on spiked samples. Participation at this program is free of charge and considered as an educational tool. Comparison of the results with those of other laboratories in Europe and USA shows that the analytical methods used during this program are in accordance with all the other procedures.

Poisoning by plant material: review of human cases and analytical determination of main toxins by high-performance liquid chromatography-(tandem) mass spectrometry.

The authors have reviewed the main toxic plants responsible for human deaths throughout the world. Forty plants (genera or species) were listed in order to establish an inventory of the active molecules that could be identified, the already published analytical methods and the reported human fatal cases. In a second step, the authors have developed a general method for the detection of various toxins in whole blood by high-performance liquid chromatography coupled to mass spectrometry or tandem mass spectrometry. Sample preparation was realized by liquid-liquid extraction at pH 9.5 for oleandrine, taxol and the alkaloids. These latter compounds were divided into two groups following their chemical properties and could be subsequently purified by acid/base clean up. Cyanogenic compounds and atractyloside were isolated by precipitation of the protein content with acetone and purified for atractyloside by washing with chloroform. Separation of the drugs occurred under reversed-phase conditions on a C18 analytical column 150x2 mm I.D. (5 microm particle size) using two different mobile phases. The first one, formiate buffer 2 mM acidified at pH 3.0, was used for the separation of atractyloside, oleandrine, taxol, the cyanogenic molecules and some alkaloids. The second mobile phase, formiate buffer 10 mM made basic at pH 8.2 was used for the majority of other alkaloids. A gradient elution mode was chosen using acetonitrile or acetonitrile-methanol (50:50, v/v) as the eluting solvent. Detection under positive ionization mode was the mode of choice for all compounds except for atractyloside (negative ions) and for taxol (mixed mode available). Application to real forensic cases has been demonstrated.

Testing hair for pharmaceuticals.

More than hundred pharmaceuticals, drugs of abuse or doping agents have been reported to be detectable in human hair. This article reviews the analysis of 90 drugs and drug metabolites by chromatographic procedures, including the pretreatment steps, the extraction methods, the reported limits of detection and the measured concentrations in real human hair samples. Some progress is observed in the detection of low dose drugs, like fentanyl or flunitrazepam. The general tendency in the last years, to highly sophisticated techniques (GC-MS-NCI, HPLC-MS, GC-MS-MS) illustrates well this constant fight for sensitivity. Some new findings, based on the recent experience of the authors, are also added.

Gas chromatographic-tandem mass spectrometric determination of anabolic steroids and their esters in hair. Application in doping control and meat quality control.

We have developed a powerful and simple sensitive method for testing hair for anabolic steroids and their esters. A 100-mg amount of powdered hair was treated with methanol in an ultrasonic bath for extraction of esters, then alkaline digested with 1 M NaOH for an optimum recovery of other drugs. The two liquid preparations were subsequently extracted with ethyl acetate, pooled, then finally highly purified using a twin solid-phase extraction on amino and silica cartridges. The residue was derivatized with N-methyl-N(trimethylsilyl)-trifluoracetamide (MSTFA) prior to injection. Analysis was conducted by gas chromatography coupled to a triple quadrupole mass spectrometer. The generally chosen parent ion was the molecular ion while two daughter ions were selected for each compound with collision energies ranging from -16 to -21 eV. Internal standards were nandrolone d3 for non-esterified drugs and testosterone phenyl propionate for esters. The limits of detection calculated from an analysis of the blanks (n=30) were 0.08 pg/mg for nandrolone, 6.20 pg/mg for boldenone, 0.07 pg/mg for methyl testosterone, 0.15 pg/mg for ethinyl estradiol, 2.10 pg/mg for metandienone, 0.86 pg/mg for testosterone propionate, 0.95 pg/mg for testosterone cypionate, 1.90 pg/mg for nandrolone decanoate, 3.10 pg/mg for testosterone decanoate and 4.80 pg/mg for testosterone undecanoate. Application to doping control has been demonstrated. In a series of 18 sportsmen, two tested positive for anabolic steroids in hair whereas urinalysis was negative for both of them. The first positive case was nandrolone and the second case concerned the identification of testosterone undecanoate. Measured in 10 white males aged between 22 and 31 years, the testosterone concentration was in the range 1.7-9.2 pg/mg (mean=5.0 pg/mg). The method was also applied in meat quality control. Of the 187 analyses realized based upon hair and urine sampling in slaughter houses, 23 were positive for anabolic steroids in hair: one case for boldenone, one case for metandienone, two cases for testosterone propionate, three cases for nandrolone, five cases for testosterone decanoate and 11 cases for methyl testosterone. In the meantime, urinalysis was always negative for these drugs or their metabolites.

[Acute poisoning during substitution therapy based on high-dosage buprenorphine. 29 clinical cases--20 fatal cases]. / Intoxications aiguës par traitement substitutif à base de buprénorphine haut dosage. 29 observations cliniques--20 cas mortels.

OBJECTIVES: Buprenorphine has been an important advance in care for drug abusers, but the toxic risk may be fatal. We report here two original series of buprenorphine poisoning in opiate abusers on substitution therapy. PATIENTS: The first series included 20 males and 9 females, aged 20-35 years (mean = 27.5) with non-fatal poisoning. The second series included 20 subjects (19 males, 1 female) aged 14-48 years (mean = 26.6) with a fatal outcome. All subjects were opiate addicts taking high-dosage sublingual buprenorphine formulation as substitution therapy. RESULTS: Blood concentrations of buprenorphine were found in all cases to remain at a low level (1.0-2.3 ng/ml, m = 1.4 ng/ml, and 1.1-29.0 ng/ml, m = 8.4 ng/ml in non-fatal and fatal cases respectively). Almost all cases involved concomitant intake of psychotropic medications, especially benzodiazepines (18 non-fatal and 17 fatal cases). DISCUSSION: These observations confirm previously reported data on the danger of buprenorphine-benzodiazepine combinations. Intravenous injection of crushed tablets also appears to be a risk factor (8 deaths and 10 non-fatal poisonings). This series highlights the need for improvement in the recently developed French program for substitution therapy with high-dosage buprenorphine in heroin addicts.