Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Control of rumen methanogenesis

During the last decades, considerable research on methane production in the rumen and its inhibition has been carried out. Initially, as methane production represents a significant loss of gross energy in the feed (2–15%), the ultimate goal of such intervention in rumen fermentation was an increase in feed efficiency. A second reason favouring research on methane inhibition is its role in the global warming phenomenon and in the destruction of the ozone layer. In this review, the authors describe briefly several interventions for reducing methane emission by ruminants. The objective can be reached by intervention at the dietary level by ration manipulation (composition, feeding level) or by the use of additives or supplements. Examples of additives are polyhalogenated compounds, ionophores and other antibiotics. Supplementation of the ration with lipids also lowered methanogenesis. More biotechnological interventions, e.g., defaunation, probiotics and introduction of reductive acetogenesis in the rumen, are also mentioned. It can be concluded that drastic inhibition of methane production is not unequivocally successful as a result of several factors, such as: instantaneous inhibition often followed by restoration of methanogenesis due to adaptation of the microbes or degradation of the additive, toxicity for the host animal, negative effects on overall digestion and productive performance. Therefore, methanogenesis and its inhibition cannot be considered as a separate part of rumen fermentation and its consequences on the animal should be taken into account.     

Floristics, performance and prognosis of historical trees in the urban forest of Guangzhou City (China)

Outstanding historical trees embedded in cities constitute pertinent environmental assets, yet they are widely threatened in third-world cities. Inadequate understanding of this valuable natural-cum-cultural heritage hinders proper conservation. A case study of Guangzhou in south China evaluated floristic composition, age profile and biomass structure of historical trees, assessed their performance in major habitats (institutional, park and roadside), and established a prognosis for future growth and management. The 348 historical trees examined belonged to only 25 species, vis-à -vis 254 trees in the entire urban forest, dominated by five species and native members. Roadside had more trees, followed by institutional and park, with merely the most common four species shared by all habitats. The limited commonality reflected tree-performance differentiation by habitats exerting selection pressure on species. The institutional growth-regime was more conducive to nurturing high-caliber specimens, whereas park is less capable. Individual species achievement by habitats, derived from tree-count ranking and relative-abundance indices, could inform species choice and tree conservation. Few trees exceeded 300 years of age in the millennium-old city, echoing a history of intense tree—city conflicts. Potential life-span, trunk and crown diameters indicated ample opportunities for further expansion of biomass and landscape impacts, which would be straitjacketed by the tightening urban fabric.     

Environmental and biological monitoring of methyl ethyl ketone (MEK)

This study was conducted to evaluate the usefulness of various biological parameters for monitoring of workers exposed to methyl ethyl ketone (MEK). Fifty male workers from a large magnetic videotape factory participated in this study. Personal air samples were collected using 3M organic vapor monitors and analysed for MEK by gas chromatography with flame ionisation detector (FID). 10 mL of urine; blood (1 mL) and exhaled air were also collected at the end of an 8-hour workshift. The headspace GC method was applied for measurement of urinary and blood MEK. MEK in expired air was analysed directly by using a GC/FID.The correlation coefficients (r) between environmental MEK and all other biological parameters measured show significant positive relationships. The r for environmental MEK and urine MEK was 0.84; for blood 0.73 and for breath 0.64. The correlation coefficients between blood and urine was 0.72; blood and breath was 0.88 and urine and breath 0.60. These findings suggest that measurements of unmetabolised MEK in blood, exhaled air and urine can be used for biological monitoring of MEK exposure. Nevertheless, laboratory methodological assessment is in favour of measuring urinary MEK as it is non-invasive and does not have to be analysed immediately after collection.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.     

The fate of fipronil in modular estuarine mesocosms

The degradation and corresponding product manifold for the pesticide fipronil was determined in three replicate estuarine mesocosms. Aqueous fipronil concentrations rapidly decreased over the 672 h timescale of the experiment (95% removal). Loss was apparently first-order in fipronil, although there appeared to be a change in the removal mechanism after 96 h that corresponded to a dramatic slowdown in its disappearance. The reduction product of fipronil, fipronil sulfide, was not detected in the water column; however, it formed rapidly in sediments and was identified as the major product of fipronil degradation in the system (20% yield at 672 h, with respect to initial fipronil concentration). Fipronil sulfone is thought to form primarily via biological oxidation; and, although it was generated rapidly in the water column (10% yield), only trace amounts were detected in the sediment (1% yield). The direct photolysis product of fipronil, fipronil desulfinyl, was present in all samples; it formed rapidly in the water column (4% yield) and partitioned into the sediment phase (7% yield) over the course of the experiment. The mass balance on fipronil and associated products was 42% at 672 h.     

Using improved neural network model to analyze RSP,NOx and NO2 levels in urban air in Mong Kok,Hong Kong

As the health impact of air pollutants existing in ambient addresses much attention in recent years, forecasting of airpollutant parameters becomes an important and popular topic inenvironmental science. Airborne pollution is a serious, and willbe a major problem in Hong Kong within the next few years. InHong Kong, Respirable Suspended Particulate (RSP) and NitrogenOxides NO_x and NO₂ are major air pollutants due to thedominant diesel fuel usage by public transportation and heavyvehicles. Hence, the investigation and prediction of the influence and the tendency of these pollutants are ofsignificance to public and the city image. The multi-layerperceptron (MLP) neural network is regarded as a reliable andcost-effective method to achieve such tasks. The works presentedhere involve developing an improved neural network model, whichcombines the principal component analysis (PCA) technique and theradial basis function (RBF) network, and forecasting thepollutant levels and tendencies based in the recorded data. Inthe study, the PCA is firstly used to reduce and orthogonalizethe original input variables (data), these treated variables arethen used as new input vectors in RBF neural network modelestablished for forecasting the pollutant tendencies. Comparingwith the general neural network models, the proposed modelpossesses simpler network architecture, faster training speed,and more satisfactory predicting performance. This improvedmodel is evaluated by using hourly time series of RSP, NO_x and NO₂ concentrations collected at Mong Kok Roadside Gaseous Monitory Station in Hong Kong during the year 2000. By comparing the predicted RSP, NO_x and NO₂ concentrationswith the actual data of these pollutants recorded at the monitorystation, the effectiveness of the proposed model has been proven.Therefore, in authors' opinion, the model presented in the paper is a potential tool in forecasting air quality parameters and hasadvantages over the traditional neural network methods.