Quantitative monitoring of dermal and inhalation exposure to 1,6-hexamethylene diisocyanate monomer and oligomers

Respiratory sensitization and occupational asthma are associated with exposure to 1,6-hexamethylene diisocyanate (HDI) in both monomeric and oligomeric forms. The monomer and polymers of diisocyanates differ significantly in their rates of absorption into tissue and their toxicity, and hence may differ in their contribution to sensitization. We have developed and evaluated a liquid chromatography/mass spectrometry (LC-MS) method capable of quantifying HDI and its oligomers (uretidone, biuret, and isocyanurate) in air, tape-stripped skin, and paint samples collected in the automotive refinishing industry. To generate analytical standards, urea derivatives of HDI, biuret, and isocyanurate were synthesized by reaction with 1-(2-methoxyphenyl)piperazine and purified. The urea derivatives were shown to degrade on average by less than 2% per week at -20 degrees C over a 2 month period in occupational samples. The average recovery of HDI and its oligomers from tape was 100% and the limits of detection were 2 and 8 fmol microl(-1), respectively. Exposure assessments were performed on 13 automotive spray painters to evaluate the LC-MS method and the sampling methods under field conditions. Isocyanurate was the most abundant component measured in paint tasks, with median air and skin concentrations of 2.4 mg m(-3) and 4.6 microg mm(-3), respectively. Log-transformed concentrations of HDI (r = 0.79, p < 0.0001) and of isocyanurate (r = 0.71, p < 0.0001) in the skin of workers were correlated with the log-transformed product of air concentration and painting time. The other polyisocyanates were detected on skin for less than 25% of the paint tasks. This LC-MS method provides a valuable tool to investigate inhalation and dermal exposures to specific polyisocyanates and to explore relative differences in the exposure pathways.     

Factors affecting variability in the urinary biomarker 1,6-hexamethylene diamine in workers exposed to 1,6-hexamethylene diisocyanate

Although urinary 1,6-hexamethylene diamine (HDA) is a useful biomarker of exposure to 1,6-hexamethylene diisocyanate (HDI), a large degree of unexplained intra- and inter-individual variability exists between estimated HDI exposure and urine HDA levels. We investigated the effect of individual and workplace factors on urine HDA levels using quantitative dermal and inhalation exposure data derived from a survey of automotive spray painters exposed to HDI. Painters' dermal and breathing-zone HDI-exposures were monitored over an entire workday for up to three separate workdays, spaced approximately one month apart. One urine sample was collected before the start of work with HDI-containing paints, and multiple samples were collected throughout the workday. Using mixed effects multiple linear regression modeling, coverall use resulted in significantly lower HDA levels (p = 0.12), and weekday contributed to significant variability in HDA levels (p = 0.056). We also investigated differences in urine HDA levels stratified by dichotomous and classification covariates using analysis of variance. Use of coveralls (p = 0.05), respirator type worn (p = 0.06), smoker status (p = 0.12), paint-booth type (p = 0.02), and more than one painter at the shop (p = 0.10) were all found to significantly affect urine HDA levels adjusted for creatinine concentration. Coverall use remained significant (p = 0.10), even after adjusting for respirator type. These results indicate that the variation in urine HDA level is mainly due to workplace factors and that appropriate dermal and inhalation protection is required to prevent HDI exposure.     

Quantitative determination of hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate (2,6-TDI) monomers at ppt levels in air by alkaline adduct coordination ionspray tandem mass spectrometry

Occupational exposures to isocyanates can lead to occupational asthma. Once sensitized, some workers could react to isocyanate monomers at concentrations below 1% of the Permissible Exposure Limit of 5 ppb in air. Currently available methods are not sufficiently sensitive to adequately evaluate isocyanates present at these levels in workplace air. This article describes a novel method for isocyanate determination allowing the ultratrace quantification in workplace air of hexamethylene diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate monomers. Sampling is performed during a complete workshift at a flow rate of 1 L min(-1) with a cassette containing a 1-(2-methoxyphenyl)piperazine-impregnated 25 mm filter. Analysis is performed using liquid chromatography hyphenated with coordination ionspray tandem mass spectrometry. The analytical method's linearity was measured for a concentration range varying from the limit of detection of 0.04-0.13 ng mL(-1), depending on the monomer, up to approximately 32 ng mL(-1) for every isocyanate monomer, all with correlation coefficients (R(2)) greater than 0.999. The analytical method's lower limit of quantification combined with an adapted sampling strategy allow the quantification of isocyanate monomers down to 0.04 ppt for an 8 h work shift when a lithium adduct is used, which is more than 300 times lower than the most sensitive method currently available. This novel method can be used to confirm the very low level of isocyanate monomers for the safe reassignment of sensitized workers and it is also useful for charting the isocyanate dispersion tail in workplace environments.     

Enantiomer ratios,patterns and levels of toxaphene congeners in human milk from Germany

High resolution gas chromatography (HRGC) coupled to quadrupole negative ion chemical ionization (NICI) mass spectrometry (MS) was used to investigate congener patterns, levels and enantiomer distribution of selected toxaphene congeners (#26, #41, #44, #50, #63, B7-1453) in human milk from Germany. #50 and #26 were the most abundant congeners. Furthermore, the identification of B7-1453, B8-1412, #41, #42, #44 and #63 was possible. Levels for the sum of #26, #41, #44 and #50 ranged from 7 to 24 microg kg(-1) milk fat and contributed between 2 and 9% to the total burden of investigated organochlorines such as selected compounds of the chlordane group, HCH, DDT and polychlorinated biphenyls (PCB). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Enantiomer ratios (ER) and enantiomer fractions (EF) of the abundant toxaphene congeners #26 and #50 as well as of B7-1453, #41 and #63 were determined. Greatest deviations from a racemic composition in individual human milk samples were found for #41 (1.54-2.37), #50 (1.37-1.72) and #63 (0.53-0.71) whereas ERs for #26 were close to 1. Compared to wildlife biota such as fish and raptors ER changes were more pronounced in human milk but comparable to human adipose tissue.     

An FTIR investigation of isocyanate skin absorption using in vitro guinea pig skin

Isocyanates may cause contact dermatitis, sensitization and asthma. Dermal exposure to aliphatic and aromatic isocyanates can occur in various exposure settings. The fate of isocyanates on skin is an important unanswered question. Do they react and bind to the outer layer of skin or do they penetrate through the epidermis as unreacted compounds? Knowing the kinetics of these processes is important in developing dermal exposure sampling or decontamination strategies, as well as understanding potential health implications such exposure may have. In this paper the residence time of model isocyanates on hairless guinea pig skin was investigated in vitro using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry. Model isocyanates tested were octyl isocyanate, polymeric hexamethylene diisocyanate isocyanurate (pHDI), polymeric isophorone diisocyanate isocyanurate (pIPDI) and methylenediphenyl diisocyanate (MDI). Isocyanates in ethyl acetate (30 microL) were spiked directly on the skin to give 0.2-1.8 micromol NCO cm(-2) (NCO = -N=C=O), and absorbance of the isocyanate group and other chemical groups of the molecule were monitored over time. The ATR-FTIR findings showed that polymeric isocyanates pHDI and pIPDI may remain on the skin as unreacted species for many hours, with only 15-20% of the total isocyanate group disappearing in one hour, while smaller compounds octyl isocyanate and MDI rapidly disappear from the skin surface (80+% in 30 min). Isocyanates most likely leave the skin surface by diffusion predominantly, with minimal reaction with surface proteins. The significance of these findings and their implications for dermal exposure sampling and isocyanate skin decontamination are discussed.     

Large and mesoscale meteo-oceanographic patterns in local responses of biogeochemical concentrations

Investigations surrounding the variability of productivity in upwelling regions are necessary for a better understanding the physical-biological coupling in these regions by monitoring systems of environmental impacts according to the needs of the regional coastal management. Using a spatial and temporal database from National Centers for Environmental Prediction (NCEP) and National Center for Atmospheric (NCAR) Research reanalysis, Quick Scatterometer vector wind, and surface stations from the Southeast coast of Brazil, we investigate the meteorological influences due to the large-scale systems in the variability of the nutrient and larvae concentration, and chlorophyll a, describing statistically relationships between them in upwelling regions. In addition, we used multivariate analysis, such as PCA and clustering to verify spatial and temporal variances and describe more clear the structure and composition of the ecosystem. Correlation matrix analyses were applied for different water masses present in the study area to identify the relations between physical and biogeochemical parameters in a region, where frequently upwelling occur. Statistical approaches and seasonal variability show that the period of November to March is more sensitive to nutrients (1.20?mg/m(3) for chlorophyll a, 2.20?μmol/l for total nitrogen and 5.5?ml/l for DO) and larvae concentrations (120 org/m(3) for most of the larvae, except for cirripedia that presented values around 370 org/m(3)) relating to the influence of large and mesoescale meteorological patterns. The spatial and temporal variables analyzed with multivariate approach show meaningful seasonality variance of the physical and biological samples, characterizing the principal components responsible for this variance in spring and summer (upwelling period), emphasizing the monitoring of species as crustaceans and mussels that are present in the local economy. Then, the spring and summer season are characterized by high productivity due to the occurrence of upwelling in this period.     

Transversal immission patterns and leachability of heavy metals in road side soils

Today there is consensus concerning the road traffic's role as a metal source. However, there are so far only a few studies which focus on the road side immission patterns regarding distance from roads, and especially in combination with the leachability of heavy metals down the soil profile. In this study, the aim was to analyse concentrations of traffic related metals in road side soils, at different depths and distances from roads, both to analyse the immission patterns as well as to explain the importance of the road construction design of the road side terrain. The BCR sequential extraction procedure was performed to be able to address the environmental risk in terms of metal mobility. Approximately 80 soil samples were analysed for seven metals; antimony (Sb), cadmium (Cd), copper (Cu), chromium (Cr), lead (Pb), nickel (Ni) and zinc (Zn). The results showed that, depending on metal, the total metal concentrations in road side soils have increased 3-16 times compared to regional background during the last decades. Each metal had a limited dispersal distance from the roads as well as down in the soil profile and the road construction significantly affected the metal immission distance. Elevated metal concentrations were mostly found for top soils and down to 10 cm in the soil profiles. The labile fractions counted for more than 40% of the total concentrations for Cd, Cu, Ni, Pb and Zn, indicating a potential mobilization of the metals if the road side soils become disturbed. The present soil metal concentration levels are not alarming, but metals with a high accumulation rate might gradually be an upcoming problem if nothing is done to their emission sources.     

Characteristic occurrence patterns of micropollutants and their removal efficiencies in industrial wastewater treatment plants

The concentrations and removal efficiencies of various kinds of micropollutants were investigated and the relationships between the input sources of industrial wastewater and occurrence patterns of each micropollutant were identified at nine on-site industrial wastewater treatment plants (WWTPs). The distribution pattern of each compound varied according to the WWTP type and several micropollutants were significantly related with specific industries: chlorinated phenols (ClPhs) with paper and metal industries, polycyclic aromatic hydrocarbons (PAHs) with petrogenic- and pyrogenic-related industries, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with the paper industry, and chlorinated benzenes (ClBzs) with dye-related industries. The activated sludge (AS) process was very efficient in the removal of ClPhs and PAHs, and the filtration process in the removal of PCDD/Fs and 1,4-dioxane. Generally, the removal efficiencies of each micropollutant varied according to the WWTP type.     

Climatology of atmospheric circulation patterns of Arabian dust in western Iran

Being in vicinity of vast deserts, the west and southwest of Iran are characterized by high levels of dust events, which have adverse consequences on human health, ecosystems, and environment. Using ground based dataset of dust events in western Iran and NCEP/NCAR reanalysis data, the atmospheric circulation patterns of dust events in the Arabian region and west of Iran are identified. The atmospheric circulation patterns which lead to dust events in the Arabian region and western Iran were classified into two main categories: the Shamal dust events that occurs in warm period of year and the frontal dust events as cold period pattern. In frontal dust events, the western trough or blocking pattern at mid-level leads to frontogenesis, instability, and air uplift at lower levels of troposphere in the southwest of Asia. Non-frontal is other pattern of dust event in the cold period and dust generation are due to the regional circulation systems at the lower level of troposphere. In Shamal wind pattern, the Saudi Arabian anticyclone, Turkmenistan anticyclone, and Zagros thermal low play the key roles in formation of this pattern. Summer and transitional patterns are two sub-categories of summer Shamal wind pattern. In summer trough pattern, the mid-tropospheric trough leads to intensify the surface thermal systems in the Middle East and causes instability and rising of wind speed in the region. In synthetic pattern of Shamal wind and summer trough, dust is created by the impact of a trough in mid-levels of troposphere as well as existing the mentioned regional systems which are contributed in formation of summer Shamal wind pattern.     

Analysis of patterns and ecological security trend of modern oasis landscapes in Xinjiang, China

Ecological security has become so important that it will affect the national security and social sustainable development. In this paper, a case study on the ecological security indexes of modern oasis landscapes in Beitun Oasis, Xinjiang, was carried out. The spatial neighbouring parameters, such as the contiguous length, measure of area and patch quantity of oasis landscape patches, affected by desert landscape patches were calculated by using GIS-based buffer analysis, the method of calculating ecological security indexes of oasis landscape was developed, and the dynamic changes of patterns and ecological security indexes of the oasis landscapes since recent 30 years were analyzed. The results showed that soil salinization or alkalization and paludification were major factors affecting the ecological security in Beitun Oasis. Therefore, measures should be taken actively to prevent and control secondary salinization and paludification. The ecological security indexes of the oasis landscape in 1972, 1990 and 2005 were 78.91, 82.28 and 83.86, respectively, which showed the degree of security is improving, and the environment was developing harmoniously between human and nature. The methods of evaluating ecological security based on the spatial neighbouring relations between landscape patches can be used to reflect preliminarily the ecological security patterns of landscapes.     

Spatial and temporal patterns of dissolved nitrogen and phosphorus in surface waters of a multi-land use basin

Research on relationships between dissolved nutrients and land-use at the watershed scale is a high priority for protecting surface water quality. We measured dissolved nitrogen (DN) and ortho-phosphorus (P) along 130 km of the Calapooia River (Oregon, USA) and 44 of its sub-basins for 3 years to test for associations with land-use. Nutrient concentrations were analyzed for spatial and seasonal patterns and for relationships with land-use and stream discharge. Ortho-P and DN were higher in lower-elevation sub-basins dominated by poorly drained soils and agricultural production compared with higher-elevation sub-basins dominated by well-drained soils and forests. Eight lower basins had at least one sample period with nitrate-N?>?10 mg L^?1. The Calapooia River had lower concentrations of dissolved nutrients compared with lower sub-basins, often by an order of magnitude. Dissolved organic N represented a greater proportion of DN in the upper forested sub-basins. Seasonal nutrient concentrations had strong positive correlations to the percent of a sub-basin that was managed for agriculture in all seasons (p?values?≤?0.019) except summer. Results suggest that agricultural lands are contributing to stream nutrient concentrations. However, poorly drained soils in agricultural areas may also contribute to the strong relationships that we found between dissolved nutrients and agriculture.     

Phytoplankton patterns along a series of small man-made reservoirs in Kenya

We studied nine small man-made reservoirs located in different climate regions of Kenya to get an insight into the relationship between phytoplankton community structure and its environment. The investigated ponds form three groups of three reservoirs each found in the rural areas of Machakos district, Mount Kenya region, and Lake Victoria area with varied climatic characteristics. The ponds were sampled in monthly intervals between May 2007 and June 2008 for physicochemical variables including water chemistry, phytoplankton community composition, zooplankton abundance, and bacterial numbers. All ponds were classified as hypertrophic. Seasonal changes were reflected in the phytoplankton pattern, as all ponds showed a community shift after the short dry season in February. Due to high nutrient loads and increased turbidity, Cyanobacteria, which were initially thought to be predominating in all investigated water bodies, were found to play only a minor role except for the Bomet reservoir in Lake Victoria region. Instead, Chloro- and Streptophyta, Dinophyta, and Euglenophyta were abundant in the pelagial. A principal component analysis explained around 85 % of the data variance with four principal components (PCs) interpreted as “location”, “ions”, “zooplankton”, and “particulate matter”. A clear separation of ponds with and without cattle access based on algal species community data was found indicating the need for a sustainable use and regular monitoring program as the local population is largely dependent on these sensitive small-scale ecosystems.     

Concentration of heavy metals in hair and skin of silver and red foxes (Vulpes vulpes)

The structure of hair and levels of main chemical elements (C, N, O, S, Cl, Ca, P, Al, Na) in the external layer of hair of silver and red foxes (Vulpes vulpes) in a non-industrialised, typically agricultural region of middle-west Poland was assessed using a scanning microscope. Additionally, analysis of the accumulation of certain heavy metals (Cr, Cu, Ni, Pb and Zn) in hair (washed) and skin (non-tanned) of those foxes was conducted. Heavy metal levels were determined using a spectrophotometric method (ICP-OES), and correlations between these levels in hair and skin were calculated. The microscopic external (morphological) and internal structures (histological) of the hair of farm and wild foxes were not differentiated; however, the hair of farm foxes (external layer) contained higher amounts of C, Na, Al and P. A significantly higher Pb content was noted in non-tanned skin of wild foxes in comparison to farm ones. In the case of farm foxes, a significantly higher Zn content in hair and Zn and Cu in skin was observed in comparison to wild ones. Positive significant correlations between Cr and Ni content (r = 0.622) and Zn and Cu (r = 0.721) in fox skin were noted. A similar relationship between Cr content in hair and Ni in skin (r = 0.643) and between Zn in hair and skin (r = 0.595) was also observed.     

Analytical approaches to the determination of phosphorus partitioning patterns in sediments

Three methods for phosphorus fractionation in sediments based on chemical extractions have been applied to fourteen aquatic sediment samples of different origin and characteristics. Two of the methods used different approaches to obtain the inorganic fractions. The Hieltjes and Lijklema procedure (HL) uses strong acids or bases, whereas the Golterman procedure (G) uses chelating reagents. The third one, the Standards, Measurements and Testing (SMT) protocol, was proposed in the frame of the SMT Programme (European Commission) which aimed to provide harmonisation and the validation of such methodologies. This harmonised procedure was also used for the certification of the extractable phosphorus contents in a sediment certified reference material (CRM BCR 684). Principal component analysis (PCA) was used to group sediments according to their composition and the three extraction methods were applied to the samples including CRM BCR 684. The data obtained show that there is some correlation between the results from the three methods when considering the organic and the residual fractions together. The SMT and the HL methods are the most comparable, whereas the G method, using a different type of reagent, yields different distribution patterns depending on sample composition. In relation to the inorganic phosphorus, the three methods give similar information, although the distribution between non-apatite and apatite fractions can be different.     

Analysis of spatial and temporal water pollution patterns in Lake Dianchi using multivariate statistical methods

Various multivariate statistical methods including cluster analysis (CA), discriminant analysis (DA), factor analysis (FA), and principal component analysis (PCA) were used to explain the spatial and temporal patterns of surface water pollution in Lake Dianchi. The dataset, obtained during the period 2003–2007 from the Kunming Environmental Monitoring Center, consisted of 12 variables surveyed monthly at eight sites. The CA grouped the 12 months into two groups, August–September and the remainder, and divided the lake into two regions based on their different physicochemical properties and pollution levels. The DA showed the best results for data reduction and pattern recognition in both temporal and spatial analysis. It calculated four parameters (TEMP, pH, COD_Mn, and Chl-a) to 85.4% correct assignment in the temporal analysis and three parameters (BOD, NH 2009/11/20Heavy metals (Cd, Cu, Fe, Mn and Zn) concentrations were determined in different tissues (muscle, kidney, liver, brain, gonads, heart and feathers) of Glaucous Gulls (Larus hyperboreus) from Bjørnøya and Jan Mayen. The age and spatial dependent variations in heavy metals were quantified and interpreted in view of the three chemometric techniques, i.e. non-parametric Mann–Whitney U test, redundancy gradient analysis and detrended correspondence analysis. The Glaucous Gulls from Bjørnøya contained significantly higher (p?<?0.05) levels of Cd, Cu and Zn than those inhabited Jan Mayen. Adult birds were characterized by greater (p?<?0.01) concentration of muscle, hepatic and renal heavy metals in comparison to chicks. Insignificantly higher slope constant Zn/Cd for the liver than for the kidney may reflect insignificant Cd exposure. Estimate of transfer factor (TF) allows us to assess variations in heavy metal concentrations during the individual development of Glaucous Gulls. It may be stated that there is a distinct increase of bioaccumulation of all the studied metals during subsequent stages of the bird life.     

Distribution patterns of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments of the Xiangjiang River, China

We investigated the occurrence and distribution patterns of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in six sediment samples from the Xiangjiang River, Hunan Province, People’s Republic of China. Total concentrations of PCDD/Fs ranged from 876 to 497,759 (mean 160,766) ng/kg dw, the highest of which exceeded that have ever been reported for sediment samples. World Health Organization total toxicity equivalent (WHO-TEQ) concentrations in three out of six samples were significantly higher than the guidance level (21.5?ng WHO-TEQ/kg dw) suggested by Canadian Sediment Quality Guideline. A predominance of octachlorodibenzo-p-dioxin (OCDD) was observed with an average contribution of 90.8% to the total PCDD/F concentrations, while 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) was the major contributor to the PCDD/F WHO-TEQ concentrations in most of the sites. Such high levels of OCDD and HpCDD may be attributed to the presence of PCP/PCP-Na pollution, although MB-WW, agricultural straw open burning, and boilers–hazardous wastes were also the potential sources of PCDD/Fs. This is the first report for the concentrations and congener profiles of PCDD/Fs in sediment samples from the Xiangtan, Zhuzhou, and Changsha sections of the Xiangjiang River, providing scientific evidence for establishing priorities to reduce ecological risks posed by PCDD/Fs in the rapidly developing areas of Hunan Province and elsewhere.     

Spatial patterns in forest composition and standing dead red spruce in montane forests of the Adirondacks and northern Appalachians

The decline of red spruce (Picea rubens Sarg.) in montane forests of the northeastern United States has been previously reported. The objective of this study was to assess spatial patterns, if any, in standing dead red spruce stems in the Adirondacks of New York and northern Appalachians of Vermont, New Hampshire, and Maine. A stratified random sample of 19 mountains along a west to east transect in the Adirondacks and the northern Appalachians showed that the live basal area of all species was highest in the White Mountains (34.6 m² ha^–1) and lowest in the Adirondack Mountains (23.7 m² ha^–1) in the Green Mountains was significantly lower than in any other region. Intact standing dead red spruce in the Adirondack and Green Mountains (30%) was significantly higher than that in the three eastern clusters (14%). The amount of intact standing dead red spruce trees increased with elevation in only the western part of the region. With the exception of the Adirondacks, there was a greater average percent dead red spruce on the west side than on the east side of each mountain. The sum of standing dead for other tree species (average 13%) showed no statistically significant patterns with region, elevation or aspect, and was significantly lower than the amount of total dead red spruce (average 42%). The standing dead red spruce patterns we observed cannot be associated with any specific causal factors at this time.