Adsorption and desorption characteristics of methamphetamine, 3,4-methylenedioxymethamphetamine, and pseudoephedrine in soils.

This work presents, for the first time, information on the adsorption-desorption characteristics of illicit drugs and precursors in soils and an estimation of their potential bioavailability. The experiment was conducted using a batch equilibrium technique for the parent drugs methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA) and the precursor pseudoephedrine in three South Australian soils varying in physiochemical properties. The individual compounds exhibited different adsorption mechanisms in the test soils, and the results fitted better with the Freundlich isotherm model (r (2) ≥ 0.99). The maximum adsorption capacity was recorded for pseudoephedrine (2,000 µg g(-1)). However, pseudoephedrine recorded lower organic carbon normalized adsorption coefficient values (<250 mL g(-1)), lower magnitudes of Gibb's free energy change, and higher percent desorption (73-92 %) compared to methamphetamine and MDMA. The results thus showed pseudoephedrine to be the most mobile compound in the soils under study, to have the highest availability for degradation of the three compounds, and to have the highest susceptibility to biotic degradation in test soils.

Illicit drugs and the environment--a review.

Illicit drugs and their metabolites are the latest group of emerging pollutants. Determination of their concentration in environment (such as water bodies, soil, sediment, air) is an indirect tool to estimate the community level consumption of illicit drug and to evaluate potential ecotoxicological impacts from chronic low level exposure. They enter the wastewater network as unaltered drugs and/or their active metabolites by human excretion after illegal consumption or by accidental or deliberate disposal from clandestine drug laboratories. This article critically reviews the occurrence and concentration levels of illicit drugs and their metabolites in different environmental compartments (e.g., wastewater, surface waters, groundwater, drinking water, and ambient air) and their potential impact on the ecosystem. There is limited published information available on the presence of illicit drugs in the environment, reports are available mainly from European countries, UK, USA, and Canada but there is a lack of information from the remainder of the world. Although the environmental concentrations are not very high, they can potentially impact the human health and ecosystem functioning. Cocaine, morphine, amphetamine, and MDMA have potent pharmacological activities and their presence as complex mixtures in water may cause adverse effect on aquatic organisms and human health. However, there is no current regulation demanding the determination of occurrence of these emerging pollutants in treated wastewater, surface water, drinking water, or atmosphere. Thus, critical investigation on distribution pattern of this new group of emerging contaminant and their potential harmful impact on our environment needs immediate attention.

Degradation in soil of precursors and by-products associated with the illicit manufacture of methylamphetamine: implications for clandestine drug laboratory investigation.

Key precursors and by-products in the Leuckardt, Nagai and dissolving metal reductive syntheses of methylamphetamine undergo degradation in soil as a result of biotic and abiotic processes. Furthermore, methylamphetamine is a product of the degradation of 1-(1',4'-cyclohexadienyl)-2-methylaminopropane and N-formylmethylamphetamine. These findings have implications for the forensic assessment of buried residues recovered from clandestine laboratory sites because markers used to infer the synthetic methods used might be absent as a result of degradation and because methylamphetamine might be present in residues as a result of degradation rather than as a direct result of its manufacture in the laboratory.

Fate of 1-(1',4'-cyclohexadienyl)-2-methylaminopropane (CMP) in soil: route-specific by-product in the clandestine manufacture of methamphetamine.

We investigated the fate of 1-(1',4'-cyclohexadienyl)-2-methylaminopropane (CMP) in soil. CMP is the major route-specific byproduct in the clandestine manufacture of methamphetamine (MAP) by the use of excess alkali metal (e.g., lithium) in liquid ammonia, which is commonly referred to as the "Nazi method". This is one of the most common methods used in many countries for the illicit production of MAP. Knowledge on the fate of CMP in the terrestrial environment is essential to combat potential threats arising from illegal dumping of clandestine laboratory wastes. We report on the sorption-desorption, degradation, and metabolism patterns of CMP in three South Australian soils investigated in laboratory scale. CMP sorption in the test soils followed a Freundlich isotherm in the concentration range of 5 to 100µgmL(-1). Degradation studies showed that CMP was fairly unstable in both non-sterile and sterile soils, with half-life values typically less than one week. The role of biotic and abiotic soil processes in the degradation of CMP also varied significantly between the different soils, and with the length of the incubation period. Interestingly, but not surprisingly, the results showed that the CMP was not actually degraded to any simpler compounds but transformed to more persistent MAP. Thus, the main concern with Nazi method is the potential hazard from MAP rather than CMP if wastes are disposed of into the environment.

Biotic and abiotic degradation of illicit drugs, their precursor, and by-products in soil.

This study presents the first systematic information on the degradation patterns of clandestine drug laboratory chemicals in soil. The persistence of five compounds - parent drugs (methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA)), precursor (pseudoephedrine), and synthetic by-products N-formylmethylamphetamine and 1-benzyl-3-methylnaphthalene) - were investigated in laboratory scale for 1 year in three different South Australian soils both under non-sterile and sterile conditions. The results of the degradation study indicated that 1-benzyl-3-methylnaphthalene and methamphetamine persist for a long time in soil compared to MDMA and pseudoephedrine; N-formylmethylamphetamine exhibits intermediate persistence. The role of biotic versus abiotic soil processes on the degradation of target compounds was also varied significantly for different soils as well as with the progress in incubation period. The degradation of methamphetamine and 1-benzyl-3-methylnaphthalene can be considered as predominantly biotic as no measureable changes in concentrations were recorded in the sterile soils within a 1 year period. The results of the present work will help forensic and environmental scientists to precisely determine the environmental impact of chemicals associated with clandestine drug manufacturing laboratories.

Effect of chlorpyrifos on microbial biomass and activities in tropical clay loam soil.

Clay loam soil from agricultural field of Gangetic alluvial zone of West Bengal was investigated to evaluate the effect of chlorpyrifos application at field rate (0.5 mg kg(-1) soil) and 100 times of the field rate (50 mg kg(-1) soil) on soil microbial variables under laboratory conditions. Acetone-induced stress on soil microorganisms was evident in the initial stages in terms of microbial biomass carbon (MBC) content in soil and basal soil respiration (BSR) in control soil samples which received acetone only as compared to control soil without acetone. The soil MBC content increased significantly by application of chlorpyrifos. The BSR and the fluorescein diacetate hydrolysing activity (FDHA) were not adversely affected by chlorpyrifos at field rate, whilst the chemical at higher dosage significantly decreased the metabolic activities of soil microbes in terms of BSR and FDHA.

Determination of acetaldehyde in ambient air: comparison of thermal desorption-GC/FID method with the standard DNPH-HPLC method.

In this work, the experimental compatibility between the standard DNPH-HPLC method and the gas chromatographic (GC) method (without any derivatization) was investigated for the analysis of atmospheric carbonyls. In the latter case, GC analysis was made based on adsorptive enrichment on solid sorbents followed by thermal desorption. For a comparative analysis between the two methods, we quantified the concentration levels of acetaldehyde from gaseous combustion samples of different charcoal products. The acetaldehyde concentration data, measured by the HPLC method (643 +/- 1,689 ppb), were approximately 10% lower than the GC-based method (722 +/- 1,788 ppb). As such, the differences in the measured concentrations were statistically insignificant. Although the percentage difference of the two methods fell within a relatively wide range, the results obtained by the GC-based method were comparable to those of the HPLC method with significantly strong correlations. The GC-based method, if tested for certain carbonyl species such as acetaldehyde, appeared to be a suitable alternative for the HPLC method.

Analytical bias among different gas chromatographic approaches using standard BTX gases and exhaust samples.

In this study, the analytical compatibility of the gas chromatographic (GC) approach was evaluated through a cross-calibration exercise. To this end, three aromatic volatile organic compounds (VOCs: benzene, toluene, and p-xylene (BTX)) were simultaneously analyzed with four individual instrumental setups (type I = GC with MS plus solid phase microextraction (SPME) method, II = GC with flame ionization detection (FID) plus SPME, III = fast GC-FID plus SPME, and IV = GC-FID plus air server/thermal desorption (AS/TD) method). A comparison of basic quality assurance (QA) data revealed considerable differences in DL values among the methods with moderate variabilities in the intercompound sensitivity. In light of the differences in detection properties, the analytical bias involved for each methodological approach was assessed by the relative relationship between analytes and basic operating conditions. The results suggest that the analysis of environmental samples at ultra-low concentration levels (at or below ppb level) can be subject to diverse sources of bias. Although detection properties of target compounds seem to be affected by the combined effects of various factors, changes in the sample concentration levels were seen to be the most consistent under the experimental setups analyzed in this study.

Food decay and offensive odorants: a comparative analysis among three types of food.

In this study, a list of offensive odorants including reduced sulfur, carbonyls, nitrogenous, and volatile organic compounds was measured by the indirect (instrumental) method during the decay processes of three food types (snipe egg, mackerel, and squid). The strengths of the odor release were also quantified in terms of dilution-to-threshold (D/T) ratio based on the air dilution sensory test. To collect odor samples for each food type, decaying experiments were conducted in 100mL throwaway syringes for 1 month. The results showed that ammonia had the largest mean ranging from 385 ppm (fish) to 554 ppm (egg). However, most odorants generally fell in the range of 0.01-10 ppm, regardless of food type. The odor strengths measured with the suprathreshold method in terms of average D/T values increased on the order of 33,520 (egg), 202,330 (fish), and 766,330 (squid). These results were highly comparable to the patterns of odor indices derived by empirical conversion of odorant concentration data. The overall results of this study thus suggest that a unique pattern of odor release develops among different odorants as well as food type.

Reduced sulfur compounds in ambient air surrounding an industrial region in Korea.

The atmospheric concentrations of several reduced sulfur compounds (RSCs) including H(2)S, CH(3)SH, DMS, CS(2), and DMDS were measured concurrently from a series of field campaigns covering multiple locations in the surroundings of a large industrial region (August 2004 to September 2005). These field studies have been designed and undertaken to inspect the concentrations of RSCs in ambient air. The RSC concentrations were found to occur in a highly variable range. H(2)S (1.06 +/- 2.07 ppb) was found to be the most abundant RSC followed by CS(2) (0.84 +/- 0.54 ppb), DMDS (0.36 +/- 1.21 ppb), DMS (0.24 +/- 0.83 ppb), and CH(3)SH (0.11 +/- 0.23 ppb). The RSC levels measured at the study area were comparable to those observed previously from other polluted environmental settings. When these RSC data were examined further in terms of spatial (industrial vs. non-industrial sites) and seasonal (summer vs. winter seasons) grouping schemes, differences in their concentration levels were statistically insignificant in most cases. In contrast, there were fairly strong variations in temporal patterns over a diurnal cycle. If these RSC concentration data were converted to diagnose the malodor strengths, their effects were in most cases insignificant with minor contribution towards odor nuisances.

The effect of cold trap adsorbents on the gas chromatographic analysis of ambient VOCs under Peltier cooling conditions.

In this work, the relative analytical performance of the GC-based detection method was investigated with a major focus on cold trap (CT) adsorbent materials against four aromatic volatile organic compounds (VOCs) (e. g., benzene, toluene, xylene, and styrene). A series of calibration experiments were hence conducted under cryofocusing conditions formed by the Peltier cooling system in a thermal desorber (TD) unit. During the course of this study, comparative calibration datasets were acquired for each of the three CT types: (i) CT (I) = Carbopack B + Carbopack C, (ii) CT (II) = Carbopack B + Carboxen 1000, and (iii) CT (III) = Tenax TA. All calibration datasets were obtained under subambient temperature (-10 degrees C) conditions controlled by the Peltier cooling system. The reliability of the calibration data was also assessed in an ancillary experiment with the aid of the modified injection through a thermal desorber (MITD) method. The results demonstrated that the GC detection properties of different VOCs were not altered significantly between different CT applications under Peltier conditions, although relative sensitivity could be distinguished moderately depending on the CT type.

Influences of sampling volume and sample concentration on the analysis of atmospheric carbonyls by 2,4-dinitrophenylhydrazine cartridge.

In this study, the analytical bias involved in the application of the 2,4-dinitrophenylhydrazine (2,4-DNPH)-coated cartridge sampling method was investigated for the analysis of five atmospheric carbonyl species (i.e., acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde). In order to evaluate the potential bias of the sampling technique, a series of the laboratory experiments were conducted to cover a wide range of volumes (1-20 L) and concentration levels (approximately 100-2000 ppb in case of acetaldehyde). The results of these experiments were then evaluated in terms of the recovery rate (RR) for each carbonyl species. The detection properties of these carbonyls were clearly distinguished between light and heavy species in terms of RR and its relative standard error (R.S.E.). It also indicates that the studied analytical approach can yield the most reliable pattern for light carbonyls, especially acetaldehyde. When these experimental results were tested further by a two-factor analysis of variance (ANOVA), the analysis based on the cartridge sampling method is affected more sensitively by the concentration levels of samples rather than the sampling volume.

The pollution status of atmospheric carbonyls in a highly industrialized area.

The concentrations of 12 carbonyls in ambient air were measured from multiple locations of an urban area in the surroundings of a large industrial complex (August 2004 to September 2005). According to our field study, acetaldehyde (19.5+/-10.6 ppb) and formaldehyde (19.3+/-10.1 ppb) were found to be the two most abundant species followed by propionaldehyde (19.0+/-23.2 ppb), acetone (15.9+/-15.2 ppb) and butyraldehyde (13.0+/-19.8 ppb). An examination of spatial variation patterns of carbonyls, when compared between industrial sites versus non-industrial sites, indicates that the mean values for each site type are statistically insignificant in most cases. In contrast, a comparison of temporal variation patterns indicates a fairly distinctive trend with the relative enhancement during summer (over winter) and/or daytime (over nighttime). The computation of the concentration ratios between some indicative species (e.g., formaldehyde/acetaldehyde and acetaldehyde/propionaldehyde) is unique enough to describe the pollution status of carbonyl species in the study area. Moreover, the relative contribution of several offensive odorous components (e.g., acetaldehyde, propionaldehyde, and butyraldehyde) is fairly strong, while their emissions are suspected to come from a substantial use of ethanol. The results of the present study thus confirm that the acquisition of ambient carbonyl concentration data is fairly useful for distinguishing the pollution status and the associated odor-related impacts.

Investigation of carbonyl compounds in air from various industrial emission sources.

The emission concentrations of carbonyl compounds in air were quantified from a total of 195 man-made source units within 77 individual companies at a large industrial complex in Korea. The measurement data were evaluated both by absolute magnitude of concentration and by their relative contribution to malodor formation such as malodor degree (MD) derived from empirical formula. It was found that formaldehyde exhibited the highest mean concentration of 323ppb with a median value of 28.2ppb, while butyraldehyde recorded the highest contribution to odor formation with an MD value of 3.5 (186 (mean) and 9.8ppb (median)). The relative intensity of carbonyl emission, when compared by the sum of MD, showed the highest source strength from the food and beverage (industry sector) and scrubber (source unit). A comprehensive evaluation of the carbonyl data from diverse industrial facilities thus allowed us to describe the fundamental patterns of their emission.

Experimental choices for the determination of carbonyl compounds in air.

The analysis of carbonyls in ambient air has received a great deal of scientific attention with the advancement of analytical techniques and increased demand for the build-up of its data base. In this review article, we have attempted to provide some insight into the relative performance of different instrumental approaches available for the analysis of ambient carbonyls with a major emphasis on high performance liquid chromatographic and gas chromatographic methods. Reported in several international standard procedures, derivatization of carbonyls with 2,4-dinitrophenylhydrazine (2,4-DNPH) with either an impinger or cartridges is the most commonly used method of HPLC detection. In this respect, a number of alternative hydrazine reagents have also been discussed for use with HPLC. In contrast, GC methods based on the combined application of adsorptive enrichment on solid sorbents and thermal desorption are examined with regard to their suitability for carbonyl analysis in air. Particular emphasis has been directed towards the advantages and drawbacks of these different instrumental techniques for ambient carbonyls. Based on this comparative approach, we discuss the suitability for each method for carbonyl analysis.

Laboratory simulated dissipation of metsulfuron methyl and chlorimuron ethyl in soils and their residual fate in rice, wheat and soybean at harvest.

Two sulfonylurea herbicides, metsulfuron methyl (Ally 20 WP) and chlorimuron ethyl (Classic 25 WP) were evaluated for their dissipation behaviour in alluvial, coastal saline and laterite soils under laboratory incubated condition at 60% water holding capacity of soils and 30 degrees C temperature was maintained. In field study herbicides were applied twice for the control of grasses, annual and perennials broad leaves weeds and sedges in rice, wheat and soybean to find out the residual fate of both the herbicides on different matrices of respective crops after harvest. Extraction and clean up methodologies for the herbicides were standardized and subsequently analyzed by HPLC. The study revealed that the half-lives of metsulfuron methyl and chlorimuron ethyl ranged from 10.75 to 13.94 d irrespective of soils and doses applied. Field trials with rice, wheat and soybean also revealed that these two herbicides could safely be recommended for application as no residues were detected in the harvest samples.

Pencycuron dissipation in soil: effect of application rate and soil conditions.

Dissipation of the fungicide pencycuron was examined under controlled laboratory conditions in clay loam soils from rice cultivated fields of alluvial soil (Typic udifluvent) and coastal saline soil (Typic endoaquept) at field rate, twice the field rate and 10 times the field rate with and without decomposed cow manure maintained at 60% of maximum water-holding capacity (WHC) and waterlogged soil condition. The half-life values depended on the initial concentrations of pencycuron. Pencycuron, in general, degraded fastest in coastal saline soil and in soil amended with decomposed cow manure at 60% of maximum WHC of soil.