Lead (Pb), cadmium (Cd), copper (Cu) and zinc (Zn) have been measured by electrothermal atomic absorption spectrometry in various sections of the 3623 m deep ice core drilled at Vostok, in central East Antarctica. The sections were dated from 240 to 410 kyear BP (Marine Isotopic Stages (MIS) 7.5 to 11.3), which corresponds to the 3rd and 4th glacial-interglacial cycles before present. Concentrations are found to have varied greatly during this 170 kyear time period, with high concentration values during the coldest climatic stages such as MIS 8.4 and 10.2 and much lower concentration values during warmer periods, such as the interglacials MIS 7.5, 9.3 and 11.3. Rock and soil dust were the dominant sources for Pb, whatever the period, and for Zn and Cu and possibly Cd during cold climatic stages. The contribution from volcanic emissions was important for Cd during all periods and might have been significant for Cu and Zn during warm periods.
The long-recognized risk to human health arising from arsenic-contaminated waters is known to be linked to partitioning reactions between arsenic and natural solid phases. Currently, the ability to predict As surface complexation is limited by the lack of molecular-level understanding of As-solid interactions. In the present study, we use density functional theory (DFT) to model mono-, bi-, and tri-dentate As(III) surface complexes on different (previously proposed) structural models for hydrated hematite, modeled as α-Fe(2)O(3)(0001)-water interfaces. One of the modeled hematite-water interfaces is terminated entirely by hydroxyl surface functional groups, comprised of hematite lattice oxygen atoms. The other hematite-water interface is an iron-terminated model in which the outermost oxygen functional groups are water (and water dissociation product) ligands. We report the DFT trends in adsorption energies in terms of As-hematite coordination, hematite surface geometry/stoichiometry, and oxygen functional group identity. The DFT energetics predict that a monodentate As(III) surface complex is preferred on both hematite-water structures, suggesting that the two structural models here employed do not sufficiently represent the true surface structure to reproduce the experimental observation of As(III) bidentate coordination. However, the results do elucidate fundamental concepts of interface reactivity: A key result, supported by electronic structure analysis, is that ligand oxygen functional groups cannot be treated on equal ground with true surface oxygen functional groups. For the systems modeled here the distinction between surface and ligand functional groups supersedes the differences in oxygen coordination with surface Fe. We discuss the impact of this finding on the application of bond-valence-based predictions of mineral-water reactivity, and use the results of this study to pose questions and directions for ongoing modeling efforts aimed at linking macroscopic reactivity with molecular-level understanding.
A procedure has been developed for the determination of iron(III) dimethyldithiocarbamate by converting it into iron(II)-bathophenanthroline complex, which is then extracted into mesityl oxide in the presence of potassium perchlorate. The absorbance is then measured at 534 nm against a reagent blank. Beer's law is obeyed over the concentration range 0.5-20 microg ml(-1) in the final solution. The method is sensitive, highly selective and can be used for the determination of ferbam in a commercial sample, and in mixtures with various dithiocarbamates (ziram, zineb, maneb, etc.) and in wheat grains.
1,2-Dichloroethane (1,2-DCA) is a raw material used for the manufacture of vinyl chloride monomer (VCM) and therefore has very often been detected in the groundwater nearby the VCM manufacturing plant. Zero-valent iron (ZVI) is capable of degrading a wide array of highly chlorinated contaminants; however, the reactivity of ZVI towards 1,2-DCA is very low. In this study, zero-valent copper nanoparticles have been synthesized for effective dechlorination of 1,2-DCA under reduction conditions of sodium borohydride. Copper nanoparticles consisted of mainly metallic copper (Cu(0)) with small amounts of cuprous oxide (Cu(2)O). They have surface areas of about 19.0 m(2) g(-1) and an average diameter of 15 nm. Batch experiments were conducted to test the effectiveness of copper nanoparticles for 1,2-DCA degradation using sodium borohydride as electron donors where the ORP was measured as -1100 mV. More than 80% of 1,2-DCA (30 mg L(-1)) was rapidly degraded within 2 h in the presence of both copper nanoparticles (2.5 g L(-1)) and borohydride (25 mM). No reduction of 1,2-DCA was observed when the system contained either copper nanoparticles alone or borohydride alone. The degradation intermediates included ethane and ethylene accounting for 79% and ∼1.5% of the 1,2-DCA lost, respectively. Potential environmental applications can be achieved by immobilizing copper nanoparticles onto the surface of reducing metals to form a reactive bimetallic structure.
A diffusive sampling method for the determination of methyl isocyanate (MIC) in air is introduced. MIC is collected using a glass fiber filter impregnated with 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ). The urea derivative formed is desorbed from the filter with acetonitrile and analyzed by means of high-performance liquid chromatography (HPLC) using fluorescence detection (FLD) with lambdaex = 471 nm and lambdaex = 540 nm. Additionally, a method was developed using tandem mass spectrometric (MS-MS) detection, which was performed as selected reaction monitoring (SRM) on the transition [MIC-NBDPZ + H]+ (m/z 307) to [NBDPZ + H]+ (m/z 250). The diffusive sampler was tested with MIC concentrations between 1 and 35 microg m(-3). The sampling periods varied from 15 min to 8 h, and the relative humidity (RH) was set from 20% up to 80%. The sampling rate for all 15 min experiments was determined to be 15.0 mL min(-1) (using HPLC-FLD) with a relative standard deviation of 9.9% for 56 experiments. At 80% RH, only 15 min sampling gave acceptable results. Further experiments revealed that humidity did not affect the MIC derivative but the reagent on the filter prior to and during sampling. The sampling rate for all experiments (including long term sampling) performed at 20% RH was found to be 15.0 mL min(-1) with a relative standard deviation of 6.3% (N = 42). The limit of quantification was 3 microg m(-3) (LC-MS-MS: 1.3 microg m(-3)) for 15 min sampling periods and 0.2 microg m(-3) (LC-MS-MS: 0.15 microg m(-3)) for 8 h sampling runs applying fluorescence detection.
The aim of this study was to investigate the relation between two toxic volatile organic compounds, 1,3-butadiene and benzene, and a commonly used indicator of vehicle exhaust fumes, NO2. This was to see if NO2 can be used to indicate personal exposure to carcinogenic substances or at least estimate ambient levels measured at a stationary point. During the winter of 2001, 40 randomly selected persons living in the City of Umeå
(in the north of Sweden) were recruited to the study. Personal measurements of 1,3-butadiene, benzene and NO2 were performed for one week, and were repeated for 20 of the 40 participants. Additional information was gathered using a diary kept by each participant. During the same time period weekly stationary measurements were performed at one urban background station and one street station in the city centre. The results from the personal measurements showed a negligible association of NO2 with 1,3-butadiene (r
= 0.06) as well as with benzene (r
= 0.10), while the correlation coefficient between 1,3-butadiene and benzene was high and significant (r
= 0.67). In contrast to the personal measurements, the stationary measurements showed strong relations between 1,3-butadiene, benzene and NO2 both within and in-between the street and urban background station. This study supports NO2 as a potential indicator for 1,3-butadiene and benzene levels in streets or urban background air, while the weak relations found for the personal measurements do not support the use of NO2 as an indicator for personal 1,3-butadiene and benzene exposure.
The aim of this study was to quantify personal exposure and indoor levels of the suspected or known carcinogenic compounds 1,3-butadiene, benzene, formaldehyde and acetaldehyde in a small Swedish town where wood burning for space heating is common. Subjects (wood burners, n = 14), living in homes with daily use of wood-burning appliances were compared with referents (n = 10) living in the same residential area. Personal exposure and stationary measurements indoors and at an ambient site were performed with diffusive samplers for 24 h. In addition, 7 day measurements of 1,3-butadiene and benzene were performed inside and outside the homes. Wood burners had significantly higher median personal exposure to 1,3-butadiene (0.18 microg m(-3)) compared with referents (0.12 microg m(-3)), which was also reflected in the indoor levels. Significantly higher indoor levels of benzene were found in the wood-burning homes (3.0 microg m(-3)) compared with the reference homes (1.5 microg m(-3)). With regard to aldehydes, median levels obtained from personal and indoor measurements were similar although the four most extreme acetaldehyde levels were all found in wood burners. High correlations were found between personal and indoor levels for all substances (r(s) > 0.8). In a linear regression model, type of wood-burning appliance, burning time and number of wood replenishments were significant factors for indoor levels of 1,3-butadiene. Domestic wood burning seems to increase personal exposure to 1,3-butadiene as well as indoor levels of 1,3-butadiene and benzene and possibly also acetaldehyde. The cancer risk from these compounds at exposure to wood smoke is, however, estimated to be low in developed countries.
Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a widely used explosive that is present in soils at a number of military sites, including training and testing ranges. Because of its relatively weak adsorption to soil, RDX frequently migrates through the unsaturated zone and causes groundwater contamination. In the environment, RDX can transform to produce mono-, di-, and tri-nitroso derivatives (MNX, DNX, and TNX) and the ring cleavage products methylenedinitramine (MEDINA) and 4-nitro-2,4-diazabutanal (NDAB). The present study was undertaken to analyze RDX and its products in groundwater samples taken from various US military sites. The stability of some of the common transformation intermediates of RDX, including the nitroso derivatives, NDAB and MEDINA, under typical conditions in a groundwater aquifer is not well understood, and appropriate preservation methods for these compounds have not been established. Therefore, we studied the inherent stability of these compounds in deionized water and in groundwater, and evaluated various preservation techniques, including adjustment of pH, temperature, and salinity. NDAB and nitroso derivatives were stable under typical ambient environmental conditions, but MEDINA was highly unstable. The addition of sea salts (10% w/v) was found to stabilize MEDINA when the samples were stored at 4 °C. Using appropriate preservation techniques, we detected nitroso derivatives and NDAB, but no MEDINA, at some of the sites investigated. Stabilizing RDX intermediate products in field samples to allow detection is important because the presence of any of these chemicals can indicate past contamination by RDX and provide insight into the occurrence of in situ natural attenuation.
Solvation descriptors have been obtained for 19 substituted 1,3,5-triazines, using literature data on water to solvent partitions, and our own experimental determinations of water to solvent partition coefficients and micellar electrokinetic chromatography (MEKC) retention factors. The solvation descriptors can then be used to predict environmentally important air to water partition coefficients, K(w), which are the reciprocal of Henry's Law constants, with due regard to units. For this class of chemistry it is shown that the values of log K(w) so obtained are generally in good agreement with the experimental values compiled in this work and also compare well with the calculated values from the established bond contribution method of Meylan and Howard as implemented in the EPI Suite, but not with calculated values from the semi-empirical quantum chemical solvation models, SM2 and SM3, recently reported by Delgado and Alderete (J. Chem. Inf. Comput. Sci., 2003, 41, 1226-1230).
An intrinsic biodegradation study involving the design and implementation of innovative environmental diagnostic tools was conducted to evaluate whether monitored natural attenuation (MNA) could be considered as part of the remedial strategy to treat an aerobic aquifer contaminated with 1,4-dioxane and trichloroethene (TCE). In this study, advanced molecular biological and stable isotopic tools were applied to confirm in situ intrinsic biodegradation of 1,4-dioxane and TCE. Analyses of Bio-Trap® samplers and groundwater samples collected from monitoring wells verified the abundance of bacteria and enzymes capable of aerobically degrading TCE and 1,4-dioxane. Furthermore, phospholipid fatty acid analysis with stable isotope probes (PLFA-SIP) of the microbial community validated the ability for microbial degradation of TCE and 1,4-dioxane. Compound specific isotope analysis (CSIA) of groundwater samples for TCE resulted in δ(13)C values that indicated likely biodegradation of TCE in three of the four monitoring wells sampled. Results of the MNA evaluation showed that enzymes capable of aerobically degrading TCE and 1,4-dioxane were present, abundant, and active in the aquifer. Taken together, these results provide direct evidence of the occurrence of TCE and 1,4-dioxane biodegradation at the study site, supporting the selection of MNA as part of the final remedy at some point in the future.
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.
Urine amine levels used as biomarkers of diisocyanate exposure have usually been normalized with creatinine concentration. The suitability of using creatinine concentration or specific gravity for these biomarkers in exposure assessment has not been established. We investigated the effect of creatinine concentration and specific gravity on urine 1,6-hexamethylene diamine (HDA) levels in multiple mixed linear regression models using quantitative dermal and inhalation exposure data derived from a survey of automotive spray painters occupationally exposed to 1,6-hexamethylene diisocyanate (HDI). Painters' dermal and breathing-zone HDI exposure were monitored for an entire workday for up to three 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. Both creatinine concentration and specific gravity were highly significant predictors (p < 0.0001) of urine HDA levels. When these two were used together in the same model, creatinine remained highly significant (p < 0.0001), but specific gravity decreased in significance (p-values 0.10-0.17). We used different individual factors to determine which affected creatinine and specific gravity. Urine collection time was a highly significant predictor of specific gravity (p = 0.003) and creatinine concentration (p = 0.001). Smoker status was significant (p = 0.026) in the creatinine model. The findings indicate that creatinine concentration is more appropriate to account for urine water content than specific gravity and that creatinine is best used as an independent variable in HDI exposure assessment models instead of traditional urine normalization with creatinine concentration.
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.
We investigated penetration patterns of monomeric and polymeric 1,6-hexamethylene diisocyanate (HDI), experimentally and as part of commercial products, in excised full-thickness human skin at 5, 10, 30, or 60 min after exposure. We observed that both monomeric and polymeric HDI were readily absorbed into the skin and that the clearcoat composition affects the penetration rate of the individual isocyanates. The short-term absorption rates for HDI monomer, biuret, and isocyanurate were determined and used to estimate the exposure time required to reach a body burden equal to the American Conference of Governmental Industrial Hygienists (ACGIH) inhalation threshold limit value (TLV) or Oregon State occupational exposure limit (OEL). Oregon is the only government entity in the United States to promulgate a short-term exposure limit (STEL) for HDI-based polyisocyanates biuret and isocyanurate. Based on these absorption rates for a slow-drying clearcoat after 10 min (1.33 μg cm(-2) h(-1)) or 60 min (0.219 μg cm(-2) h(-1)), we calculated that 6.5 and 40 min dermal exposure, respectively, is required to achieve a dose of HDI equivalent to the ACGIH TLV. For biuret, the time to achieve a dose equivalent to the Oregon OEL for slow-drying clearcoat was much shorter (<31 min) than that for fast-drying clearcoat (618 min). Isocyanurate had the shortest skin absorption times regardless of clearcoat formulation (14 s-1.7 min). These results indicate that the dose received through dermal exposure to HDI-containing clearcoats has a significant potential to exceed the dose equivalent to that received through inhalation exposure at established regulatory limits. A critical need exists to monitor dermal exposure quantitatively in exposed workers, to use proper protective equipment to reduce dermal exposure, and to re-evaluate regulatory exposure limits for isocyanates.
Accurate measurement of workplace respirable dust concentration is an essential step in eliminating lung disease in any occupational setting. In the United States (U.S.) coal mining industry, this measurement process has relied upon a personal sampler that includes a 10 mm Dorr-Oliver (DO) nylon cyclone operated at a flow rate of 2.0 L min(-1) to collect a respirable dust sample. Dust concentrations measured with this sampler are multiplied by 1.38, which was empirically derived, to convert them to measurements approximating the United Kingdom British Medical Research Council (BMRC) definition of respirable dust upon which the health effects of coal mine dust are based. The International Organization for Standardization (ISO) subsequently refined the respirable dust definition and the U.S. National Institute for Occupational Safety and Health (NIOSH) 1995 Criteria for a Recommended Standard presented a conversion multiplier of 0.857 to apply to the 2.0 L min(-1) DO (in addition to the1.38 multiplier) to obtain equivalent ISO concentrations, as approximated by the 1.7 L min(-1) DO. However, the conversion multiplier 0.857 was derived indirectly from a limited size distribution data set rather than a direct comparison of the DO samplers. The present analysis focuses on providing a more accurate conversion multiplier derived from direct comparisons of the 2.0 L min(-1) (with 1.38 BMRC equivalency multiplier) and 1.7 L min(-1) DO cyclones. A weighted linear regression analysis of this database suggests that a more accurate estimate of the conversion multiplier is 0.815.
First published as an Advance Article on the web 11th March 2004 Occupational exposure is the condition of being subjected through employment to a chemical, physical, or biological agent, or to a specific process, practice, behavior, or organization of work. Exposure to a chemical agent is typically the contact of that agent with the outer boundary of a subject, such as the respiratory system, skin, or digestive system. In occupational hygiene we are most concerned with exposure through the respiratory system, although, increasingly we are concerned with the results of dermal exposures, including those exposures to the skin that can be transferred to the mouth and digestive system. This presentation will detail methods available for assessing personal exposures to chemicals through monitoring. The results from monitoring can then be compared to established guidelines and regulations, although this is not the only rationale for making measurements. These monitoring methods are currently used around the world to establish the benchmark hazard from which risk to the worker can be predicted. The presentation will describe the general techniques for assessing exposures to the respiratory system from chemical gases and vapors, chemical dusts, and exposures to the skin from bulk chemicals or chemical contamination of surfaces. For respiratory exposures, direct-reading instruments are available for spot measurements, and for monitoring short-term fluctuations in concentration. However, most standards and regulations are based on time-integrated (time-weighted average)
Sediments were collected from the 110 mile hole and along a transect from 58 degrees 58.32' N 1 degree 10.38' W to the UK National Marine Monitoring (NMMP) site in the inner Moray Firth, for determination of hydrocarbon concentration and composition. Total PAH concentrations (2- to 6-ring PAHs, parent and branched) were highest at NMMP site 95 and at the associated end of the transect in the inner Moray Firth. PAHs in this area were of predominately pyrolytic origin and could be attributed to urban and industrial activities. The majority of sediments collected in the middle section of the transect had low total PAH concentrations (< 100 ng g(-1) dry weight). The high proportion of naphthalenes and alkylated PAHs in this area suggested a predominately petrogenic input. The GC-FID aliphatic hydrocarbon profiles showed that the majority of sediments, including those in the inner Firth, had a limited petrogenic input. This was supported by the geochemical biomarker profiles, which contained triterpanes typical of Middle Eastern crude oil. Principal component analysis was used to investigate spatial trends in the PAH distributions and demonstrated that there were differences between areas. The NMMP site 95 and transect start and middle sediments were well separated. PCA further confirmed that sediments from the NMMP site 95, the 110 mile hole and the inner Moray Firth (south west) end of the transect contained PAHs from predominately pyrolytic sources, whereas sediments from the north east end (start) and the middle of the transect were typified by a greater petrogenic component.
A field survey of antifoulant concentrations was undertaken in two UK estuaries (Hamble and Orwell) in 1998 and 1999. The two locations offered variations in physical aspects (Orwell estuary being significantly larger than the Hamble) as well as differences in boat densities (Hamble having almost twice as many vessels moored in the estuary and marinas). Samples were analysed for copper, zinc, diuron and Irgarol 1051, and were collected in summer and winter in order to identify potential seasonal variations in concentrations. The effect that different marina types (e.g. locked marina, one located in a natural inlet and pontooned ones in the open estuary) had on antifoulant concentrations were also investigated. Concentrations of the organic booster biocides, diuron and Irgarol 1051 in the marinas and estuaries were mainly influenced by leaching from antifoulant paints applied to the hulls of leisure craft, and so levels reflected the number of vessels present in the water. As a consequence significantly higher concentrations were found in marinas (up to ca. 900 ng l(-1) for diuron and 240 ng l(-1) for Irgarol 1051) compared with estuaries (up to ca. 400 ng l(-1) for diuron and 100 ng l(-1) for Irgarol 1051) and in summer compared with winter. Sediment concentrations of Irgarol 1051 and diuron were rarely detectable other than in the marinas where high concentrations were detected near slipways assumed to be derived from washed off paint chips. Dissolved concentration profiles for copper and zinc in the estuaries and marinas were different from those for the organic booster biocides partly because other sources of these metals contributed to estuarine and marina loads. In particular, riverine loads and inputs from sacrificial anodes attached to leisure craft, exhibited a major influence of estuarine levels of zinc. Consequently, only in the Hamble estuary for copper was there a clear distinction between summer (typically 3-4 microg l(-1)) and winter dissolved values (typically 1-2 microg l(-1)) that could be largely attributable to the leaching of antifoulant paints. Sediment concentrations for both metals were similar for both estuaries, with little variation between winter and summer values (Zn ranging from 28 to 614 mg kg(-1) and Cu from 6 to 1016 mg kg(-1)) as with the organic booster biocides highest levels were measured at the base of slipways in marinas.
Fate and transport of Irgarol 1051 were assessed using a modular estuarine mesocosm containing natural seawater, saltmarsh sediments, marsh grass, shrimp, clams, snails, and naturally derived planktonic and benthic microorganisms. The mesocosms were enclosed in a greenhouse under near ambient conditions, and included a saltwater sump and a simulated tidal flux. The exposure was comprised of four replicate treatments of 0, 100, 1,000 and 10,000 ng/L Irgarol. Solid-phase extraction (SPE) was used to extract Irgarol and its major metabolite M1 (aka GS26575) from water samples. Sediment samples were extracted using Accelerated Solvent Extraction (ASE) with 100% dichloromethane. Irgarol and M1 were separated and quantified utilizing Liquid Chromatography Tandem Mass Spectrometry (LC-MS-MS) with ElectroSpray Ionization in Multiple Reaction Monitoring mode. Aqueous concentrations of Irgarol declined rapidly (average 93% loss) over the course of the 35 day experiment while Irgarol was accumulated in the sediments (average mass balance of 75 +/- 5%). Loss of aqueous Irgarol occurred in two distinct phases, a relatively rapid phase up to 96 hours post-dose, and a slower phase following 96 hours. The rate constants of the initial rapid degradation phase (k(1)) for treatments 100 and 1,000 ng/L Irgarol were 2-3 times higher than the rate constants of the subsequent slow degradation phase (k(2)) for these treatments. The average half-life of Irgarol in water was 7 +/- 3 days. The aqueous concentration of Irgarol's metabolite, M1 increased over the course of the experiment. By 35 days post-dose, M1 concentrations in water averaged about 3% of the parent compound. M1 also accumulated in mesocosm sediments (average 16.7 +/- 2.5% of total Irgarol dose). Mass balance calculations showed that by 35 days, Irgarol and M1 amounts in mesocosm water and sediments were close to 100% of the initial Irgarol dose. Average partition coefficient normalized for organic carbon (log K(oc)) calculated for Irgarol was 3.2 +/- 0.1 for 35 days post-dose. Accumulation of Irgarol and M1 in mesocosm sediments may warrant further study to assess toxicity for benthic communities.
Asbestos is a naturally occurring mineral in the Earth's crust, and it is not confined to the historic and current asbestos mining areas, but rather quite commonly encountered in certain geological environments across the world. That diseases developed as a result of high exposures suffered by miners and asbestos products workers is incontrovertible. In addition, asbestos contamination as a result of past production and use is considered a serious issue where remediation is normally required. However, the risk to health of living on soil and rock where asbestos is encountered as a result of the natural occurrence of small quantities of asbestos minerals is less obvious. The picture becomes even less clear when the minerals are subject to intensive investigation, since our generally accepted definitions of asbestos are themselves put to the test. The discovery of asbestos or related minerals has consequences beyond any immediate risks to health, including profound effects on the value of and ability to use or enjoy property. This review examines the issue of naturally occurring asbestos (NOA) as it has developed in the United States of America and elsewhere, including some superficial insights into the reactions of communities to the presence of NOA. These responses to 'contamination' by nature deserve further in-depth study.
Tropical coral reefs are charismatic ecosystems that house a significant proportion of the world's marine biodiversity. Their valuable goods and services are fundamental to the livelihood of large coastal populations in the tropics. The health of many of the world's coral reefs, and the goods and services they provide, have already been severely compromised, largely due to over-exploitation by a range of human activities. These local-scale impacts, with the appropriate government instruments, support and management actions, can potentially be controlled and even ameliorated. Unfortunately, other human actions (largely in countries outside of the tropics), by changing global climate, have added additional global-scale threats to the continued survival of present-day coral reefs. Moderate warming of the tropical oceans has already resulted in an increase in mass coral bleaching events, affecting nearly all of the world's coral reef regions. The frequency of these events will only increase as global temperatures continue to rise. Weakening of coral reef structures will be a more insidious effect of changing ocean chemistry, as the oceans absorb part of the excess atmospheric carbon dioxide. More intense tropical cyclones, changed atmospheric and ocean circulation patterns will all affect coral reef ecosystems and the many associated plants and animals. Coral reefs will not disappear but their appearance, structure and community make-up will radically change. Drastic greenhouse gas mitigation strategies are necessary to prevent the full consequences of human activities causing such alterations to coral reef ecosystems.
Endocrine disruption in the aquatic environment has been a much-researched topic worldwide for the last fifteen years. We have not attempted to write a traditional review of the topic with this paper. Instead, based on unpublished reports and our own personal memories, we provide a history of the development of endocrine disruption research in the last 30 years, since the initial, accidental discovery of intersex fish in an English river in 1978. We focus on how the key questions were tackled, and the often surprising answers to some of these questions. We cover what we now know, and what we still do not know. Based on our current understanding, we emphasize the crucial role played by interdisciplinary research in moving the issue forward. The paper concludes with a selection of general messages about chemicals in the environment which have emerged from endocrine disruption research, and how these have changed our understanding of chemicals in the environment. If lessons have been learnt, and are acted upon when the next chemical 'scare' emerges (as it inevitably will), then it should be possible to act more efficiently and effectively to better protect the environment than was achieved during the "oestrogens in the environment" era.
Sustainable land management (SLM) is proposed as a unifying theme for current global efforts on combating desertification, climate change and loss of biodiversity in drylands. A focus on SLM will achieve the multiple goals of the three UN Conventions (UNCCD, UNFCCC and UNCBD) and in particular will address the roots causes of poverty and vulnerability to climate change rather than a current focus on adapting to climate change. The interlinkages between land degradation, climate change and loss of biodiversity are outlined together with a proposed set of interventions to achieve multiple goals. It is argued that improved land productivity is a viable goal to reduce poverty in drylands provided it is linked to payments for environmental services and better crop and weather insurances and coupled with alternative livelihoods that are not primarily dependent on land productivity. Obstacles to the achievement of SLM are discussed and the steps necessary to overcome them are presented. It is suggested that promoting SLM would be a better focus for the UNCCD than combating desertification.
Traditional ideas of science as being separate and separable from ideology and politics have to be reconsidered. Each interpretation of sustainable development is not only scientific but at the same time ideological. For this reason our ideas about good science should also be related to normal imperatives of democracy. Mainstream neoclassical economics is specific in scientific and ideological terms. This paradigm is useful for some purposes and has played a role as a mental map in guiding us towards economic growth and other ideas about progress in society and the economy. Sustainable development, however, represents an ideological turn in our ideas about progress and it is no longer clear that neoclassical theory will be enough. Alternative perspectives in economics are being developed as part of a pluralistic strategy and the monopoly position of neoclassical economists at university departments of economics is thereby challenged. A 'political economic person' is suggested as alternative (complement) to Economic Man assumptions and a 'political economic organization' to be compared with the neoclassical profit maximizing firm. Alternative ways of understanding markets and international trade, efficiency, decision-making, monitoring and assessment are also needed. It is argued that such an alternative mental map is useful for actors who take the challenge of sustainable development seriously.
In August, around 850 delegates from 46 countries gathered in Birmingham (UK) for the 28th International Symposium on Halogenated Persistent Organic Pollutants ('Dioxin 2008', for short). Inaugurated in Rome in 1980, this has grown to become the main research symposium worldwide for research in the field of persistent organic pollutants (POPs). This was the first time the meeting had been held in the UK, the venue being Birmingham's world-class International Convention Centre.
Public awareness about the problems related to rainforest depletion increased considerably in the 1990s, but the level of emphasis to the problems faced by the world's tropical rainforests has become conspicuously low in recent years. Yet, there is a heightened sense of urgency in respect of the need to handle the challenges posed by climate change and the role that rainforest depletion may play in this process. This paper reviews the relationships between rainforest depletion and climate change, and outlines some areas where action is needed.
The tissue-residue approach for toxicity assessment (TRA) is simply the use of tissue concentrations as the dose metric for characterizing toxicant potency. There are several advantages to using tissue residues over exposure concentrations (e.g., water, sediment, and diet) to calculate toxicity metrics. These include a large reduction in toxic response variability among all species for a given compound, an improved ability to address mixture toxicity, an increased use of information on modes and mechanisms of toxic action, a likely reduction in the number of species needed to characterize toxicant potency, the potential to improve ecological risk assessments, and the generation of more scientifically defensible tissue, water, and sediment toxicity guidelines or criteria. A keystone concept for the TRA is that the body/tissue residue reflects the target "dose" better than the traditional dose (e.g., water, air, soil/sediment, or diet) because the closer the dose surrogate is to the actual site of toxic action the less it is influenced by myriad modifying factors. Our goal for this review is to present the concepts and issues associated with the TRA and discuss some of the potential applications and expected improvements to the field of environmental toxicology that we believe will promote enhanced protection for species and ecosystems.
It is clear that mineral dust particles can impact a number of global processes including the Earth's climate through direct and indirect climate forcing, the chemical composition of the atmosphere through heterogeneous reactions, and the biogeochemistry of the oceans through dust deposition. Thus, mineral dust aerosol links land, air, and oceans in unique ways unlike any other type of atmospheric aerosol. Quantitative knowledge of how mineral dust aerosol impacts the Earth's climate, the chemical balance of the atmosphere, and the biogeochemistry of the oceans will provide a better understanding of these links and connections and the overall impact on the Earth system. Advances in the applications of analytical laboratory techniques have been critical for providing valuable information regarding these global processes. In this mini review article, we discuss examples of current and emerging techniques used in laboratory studies of mineral dust chemistry and climate and potential future directions.
Divergent scientific and regulatory agency perspectives about contaminants in fish have lead to contradictory advice and confusing public messages about its consumption. The evidence for the protective effect of eating fish on cardiovascular outcomes is considered to be convincing. It has long been attributed to n-3 unsaturated long-chain fatty acids. Persistent organic pollutants (POPs) are compounds that are lipid soluble and accumulate in the aquatic food chain. Despite a considerable decrease in their levels in fish during the last two decades, there is still significant concern about potential negative health effects and an ongoing debate exists about what type of fish consumption advisories are most suitable. In this review our aim is twofold, namely to explore: (1) the underlying causes for the conflicting recommendations by discussing the strengths and limitations of risk assessment and epidemiological evidence; and (2), the role of risk management in formulating public dietary advisories. It is our view that the latter advice is most appropriately formulated in the context of risk management, of which both epidemiologic evidence and risk assessment are essential components.
Five Wistar rats were given an intraperitoneal injection of [114mIn]InCl3 during four consecutive days. One hour after the last injection the rats were sacrificed. The in vivo distribution of 114mIn was studied in the blood and in different organs. Differential centrifugation was used to study the distribution in liver, kidney and spleen homogenate. Rat serum, packed cell lysate, urine and the cytosol of liver, kidney and spleen homogenate were examined by size exclusion fast protein liquid chromatography. The results showed that serum accounts for 90% of the indium activity in whole blood. Indium is preferentially accumulated within the liver, spleen and kidney, the highest amount of 114mIn being localised in the cytosolic fraction followed by the mitochondria. Size exclusion experiments showed that, in rat serum, indium is exclusively bound to transferrin. These results differed from earlier in vitro incubation experiments of human serum with 114mIn. It was not possible, from the experiments described herein, to conclude unequivocally whether indium is bound to haemoglobin of packed cell lysate or to another high molecular mass compound. Indium is associated with the high molecular mass fraction in liver, kidney and spleen cytosol; only in kidney are small amounts of 114mIn found in the low molecular mass fraction. The in vivo inhibitory effect of indium on the delta-aminolaevulinic acid dehydratase (ALAD) enzymatic activity in red blood cells and kidney tissue, well documented by other researchers, could not be attributed to direct binding of indium with this enzyme.
Two in vivo experiments were carried out in this study. In the first experiment five rats were given two subcutaneous injections of [(114m)In]InAs. Major sites of accumulation were spleen, liver and kidney. The intracellular distribution of indium was examined by differential centrifugation. The cytoplasmic fraction contained most of the indium activity followed by the mitochondrial fraction. Both outcomes are in close agreement with the results obtained in previous studies. Chromatographic separations on a preparative size exclusion column were carried out. It was shown that indium was mostly bound to high molecular mass compounds in serum and in the cytoplasmic fraction of spleen, liver and kidney. In a second experiment five rats were given four oral doses of [(114m)In]InAs over a short period. Prior to this experiment the in vitro solubility of cold InAs in simulated gastric fluid (SGF) and simulated intestinal fluid (SIF) was determined using graphite furnace atomic absorption spectroscopy. In the case of the SGF only 1.3% of an InAs suspension dissolved after 48 hours incubation at 37 degrees C. InAs was not soluble in SIF. Uptake of InAs after oral administration was minimal (<1%). Due to incomplete removal of traces of [(114m)In]InAs from the gastrointestinal tract, it was impossible to calculate accurately the in vivo distribution over the different organs. As the uptake and consequently the activity in the organs were very low, no further chromatographic separations could be carried out. Considering this very low uptake, it can be concluded that InAs will not accumulate in the body after oral exposure.
A peat core from an ombrotrophic bog in Switzerland provides the first complete, long-term record (14 500 years) of atmospheric Ag and Tl deposition. The lack of enrichment of Ag and Tl in the basal peat layer shows that mineral dissolution in the underlying sediments has not contributed measurably to the Ag and Tl inventories in the peat column, and that Ag and Tl were supplied exclusively by atmospheric deposition. The temporal and spatial distribution of modern peaks in Ag and Tl concentrations are similar to those of Pb which is known to be immobile in peat profiles. Silver and Tl, therefore, are effectively immobile in the peat bog also, allowing an atmospheric deposition chronology to be reconstructed. Silver concentrations vary by up to 114x and Tl up to 241x. While Holocene climate change and land use history can explain the variation in metal concentrations and enrichment factors (EF) in ancient peats (i.e. pre-dating the Roman Period), anthropogenic sources have to be invoked to explain the very high EF values (up to 123 in the case of Ag and 12 in the case of Tl) in peat samples since the middle of the 19th Century. The "natural background" EF of Tl in ancient peats is remarkably close to unity, indicating a lack of significant enrichment of this element in atmospheric aerosols due to chemical weathering of crustal rocks. Silver, on the other hand, shows a pronounced enrichment from 8030 to 5230 (14)C years BP (12x compared to crustal rocks); this may be due to weathering phenomena or biological processes, both of which are driven by climate. Even compared to the natural enrichment of Ag during the mid-Holocene, however, the enrichments of Ag and Tl in modern peats from the Industrial Period are at least an order of magnitude greater. The Pb/Ag and Tl/Ag ratios show that Pb and Tl are preferentially released, compared to Ag, during smelting of argentiferous Pb ores mined during the Roman and Medieval Periods.
A slag sample from a lead refiner has been obtained and given to two analytical laboratories to determine the release of trace elements from the sample according to BS EN 12457-2. Samples analysed by one laboratory passed waste acceptance criteria, leading it to be classified as an inert material; samples of the same material analysed by the other laboratory failed waste acceptance criteria and were classified as hazardous. It was found that the sample preparation procedure is the critical step in the leaching analysis and that the effects of particle size on leachability should be taken into account when using this standard. The purpose of this paper is to open a debate on designing a better defined standard leaching test and making current waste acceptance criteria more flexible.
Recent studies have demonstrated the utility of ultrasonic extraction (UE), followed by portable anodic stripping voltammetry (ASV), for the on-site determination of lead in environmental and industrial hygiene samples. The aim of this work was to conduct an interlaboratory evaluation of the UE-ASV procedure, with a goal of establishing estimates of method performance based on results from collaborative interlaboratory analysis. In this investigation, performance evaluation materials (PEMs) with characterized lead concentrations were used for interlaboratory testing of the UE-ASV procedure. The UE-ASV protocol examined has been promulgated in the form of two separate national voluntary consensus standards (one for UE and another for electroanalysis, which includes ASV). The PEMs consisted of characterized and homogenized paints, soils, and dusts (the last of which were spiked onto wipes meeting national voluntary consensus standard specifications), and air filter samples (mixed cellulose ester membrane) generated using characterized paints within an aerosol chamber. The lead concentrations within the PEMs were chosen so as to bracket pertinent action levels for lead in the various sample matrices. The interlaboratory evaluation was conducted so as to comply with an applicable national voluntary consensus standard that can be used to estimate the interlaboratory precision of a given analytical test method. Based on the analytical results reported by the participating laboratories, relative standard deviations (RSDs) for repeatability and reproducibility were computed for three different lead contents of the four PEMs. RSDs for repeatability were 0.019-0.100 for paints; 0.030-0.151 for soils; 0.085-0.134 for dust wipes; and 0.095-0.137 for air filters. RSDs for reproducibility were 0.127-0.213 for paints; 0.062-0.162 for soils; 0.085-0.134 for dust wipes; and 0.114-0.220 for air filters. With the exception of one of the air filter samples and one of the paint samples, the precision estimates were within the +/- 20% precision requirement specified in the US Environmental Protection Agency National Lead Laboratory Accreditation Program (NLLAP). The results of this investigation illustrate that the UE-ASV procedure is an effective method for the quantitative measurement of lead in the matrices evaluated in this study.
Liquid chromatography with hydride generation atomic absorption spectrometry as the detection system was applied to the separation and determination of inorganic tin, tributyltin, dibutyltin, monobutyltin, diphenyltin and monophenyltin. A reversed phase C18 column and a methanol/water/acetic acid (70:27:3, v/v/v) mixture containing 0.05%(v/v) triethylamine and 0.1%(w/v) tropolone as the mobile phase (isocratic elution) were used. Extraction of organotins from the samples was carried out using methanol containing 0.05%(w/v) tropolone, a process that was repeated twice. The supernatants were shaken with water and dichloromethane in a separating funnel and the organic phase was collected and evaporated to dryness. When the method was applied to the speciation of tin in fresh and canned mussels, no organotins above the detection limits were identified in any of the samples, inorganic tin being the only species detected. The reliability of the procedure was checked by analyzing the total tin content of the samples by electrothermal atomic absorption spectrometry and by speciation of tin in a certified reference material, mussel tissue (CRM 477). The method can be used for environmental monitoring of organotins contaminated samples.
Suitable techniques have been developed for the extraction of arsenic species in a variety of biological and environmental samples from the Pak Pa-Nang Estuary and catchment, located in Southern Thailand, and for their determination using HPLC directly coupled with ICP-MS. The estuary catchment comprises a tin mining area and inhabitants of the region can suffer from various stages of arsenic poisoning. The important arsenic species, AsB, DMA, MMA, and inorganic arsenic (As III and V) have been determined in fish and crustacean samples to provide toxicological information on those fauna which contribute to the local diet. A Hamilton PRP-X100 anion-exchange HPLC system employing a step elution has been used successfully to achieve separation of the arsenic species. A nitric acid microwave digestion procedure, followed by carrier gas nitrogen addition- (N2)-ICP-MS analysis was used to measure total arsenic in sample digests and extracts. The arsenic speciation of the biological samples was preserved using a Trypsin enzymatic extraction procedure. Extraction efficiencies were high, with values of 82-102%(As) for fish and crustacean samples. Validation for these procedures was carried out using certified reference materials. Fish and crustacean samples from the Pak Pa-Nang Estuary showed a range for total arsenic concentration, up to 17 microg g(-1) dry mass. The major species of arsenic in all fauna samples taken was AsB, together with smaller quantities of DMA and, more importantly, inorganic As. For sediment samples, arsenic species were determined following phosphoric acid (1 M H3PO4) extraction in an open focused microwave system. A phosphate-based eluant, pH 6-7.5, with anion exchange HPLC coupled with ICP-MS was used for separation and detection of AsIII, AsV, MMA and DMA. The optimum conditions, identified using an estuarine sediment reference material (LGC), were achieved using 45 W power and a 20 minute heating period for extraction of 0.5 g sediment. The stability and recovery of arsenic species under the extraction conditions were also determined by a spiking procedure which included the estuarine sediment reference material. The results show good stability for all species after extraction with a variability of less than 10%. Total concentrations of arsenic in the sediments from the Pak Pa-Nang river catchment and the estuary covered the ranges 7-269 microg g(-1)and 4-20 [micro sign]g g(-1)(dry weight), respectively. AsV was the major species found in all the sediment samples with smaller quantities of AsIII. The presence of the more toxic inorganic forms of arsenic in both sediments and biota samples has implications for human health, particularly as they are readily 'available'.
This research aimed to understand the sources and fate of Salmonella and fecal bacteria in urban surface waters. An urban creek (San Pedro Creek, California, USA) that had unusually high levels of Salmonella and fecal bacteria relative to other nearby waterbodies was chosen as a model field site. State of the art microbiological methods were used in concert with modeling to investigate Salmonella and fecal bacteria sources, and determine field-relevant dark inactivation and photoinactivation rates. Three along-creek surveys that spanned reaches adjacent to both urban and forested land covers were conducted to measure Salmonella, enterococci, Escherichia coli, and horse- and human-specific Bacteroidales. Salmonella were detected adjacent to and downstream of urban land cover, but not adjacent to forested land cover. No human or horse-specific Bacteroidales fecal markers were detected implicating other urban animal sources of bacteria. Two locations along the creek where Salmonella was consistently detected were sampled hourly for 25 hours and a mass-balance model was applied to determine field-relevant light and dark inactivation rates for Salmonella, enterococci, and E. coli. Sunlight inactivation did not appear to be important in modulating concentrations of Salmonella, but was important in modulating both enterococci and E. coli concentrations. Dark inactivation was important for all three organisms. This is the first study to quantitatively examine the fate of Salmonella within an urban surface water. Although the work is carried out at a single site, the methodologies are extendable to source tracking in other waterbodies. Additionally, the rate constants determined through the modeling will be useful for modeling these organisms in other surface waters, and represent useful benchmarks for comparison to laboratory-derived inactivation rates.
Researchers are now discovering that naturally occurring environmental nanoparticles can play a key role in important chemical characteristics and the overall quality of natural and engineered waters. The detection of nanoparticles in virtually all water domains, including the oceans, surface waters, groundwater, atmospheric water, and even treated drinking water, demonstrates a distribution near ubiquity. Moreover, aquatic nanoparticles have the ability to influence environmental and engineered water chemistry and processes in a much different way than similar materials of larger sizes. This review covers recent advances made in identifying nanoparticles within water from a variety of sources, and advances in understanding their very interesting properties and reactivity that affect the chemical characteristics and behaviour of water. In the future, this science will be important in our vital, continuing efforts in water safety, treatment, and remediation.
The first detectable activities of radioiodine (131)I, and radiocaesium (134)Cs and (137)Cs in the air over Central Poland were measured in dust samples collected by the ASS-500 station in the period of 21(st) to 24(th) of March, 2011. However, the highest activity of both fission products, (131)I and (137)Cs: 8.3 mBq m(-3) and 0.75 mBq m(-3), respectively, were obtained in the samples collected on 30(th) March, i.e.∼18 days after the beginning of the fission products' discharge from the damaged units of the Fukushima Daiichi Nuclear Power Plant. The simultaneously determined corrected aerosol residence time for the same samples by (210)Pb/(210)Bi and (210)Pb/(210)Po methods was equal to 10 days. Additionally, on the basis of the activity ratio of two other natural cosmogenic radionuclides, (7)Be and (22)Na in these aerosol samples, it was possible to estimate the aerosol residence time at ∼150 days for the solid particles coming from the stratospheric fallout. These data, as well as the differences in the activity size distribution of (7)Be and (131)I in the air particulate matter, show, in contrast to the Chernobyl discharge, a negligible input of stratospheric transport of Fukushima-released fission products.
The Savannah River Site was constructed in South Carolina to produce plutonium (Pu) in the 1950s. Discharges associated with these now-ceased operations have contaminated large areas within the site, particularly streams associated with reactor cooling basins. Evaluating the exposure risk of contamination to an ecosystem requires methodologies that can assess the bioavailability of contaminants. Plants, as primary producers, represent an important mode of transfer of contaminants from soils and sediments into the food chain. The objective of this study was to identify local area plants for their ability to act as bio-monitors of radionuclides. The concentrations of cesium-137 ((137)Cs), potassium-40 ((40)K), (238)Pu and (239,240)Pu in plants and their associated soils were determined using γ and α spectrometry. The ratio of contamination concentration found in the plant relative to the soil was calculated to assess a concentration ratio (CR). The highest CR for (137)Cs was found in Pinus palustris needles (CR of 2.18). The correlation of soil and plant (137)Cs concentration was strong (0.76) and the R(2) (0.58) from the regression was significant (p = 0.006). This suggests the ability to predict the degree of (137)Cs contamination of a soil through analysis of the pine needles. The (238)Pu and (239,240)Pu concentrations were most elevated within the plant roots. Extremely high CR values were found in Sparganium americanum (bur-reed) roots with a value of 5.86 for (238)Pu and 5.66 for (239,240)Pu. The concentration of (40)K was measured as a known congener of (137)C. Comparing (40)K and (137)C concentrations in each plant revealed an inverse relationship for these radioisotopes. Correlating (40)K and (137)Cs was most effective in identifying plants that have a high affinity for (137)Cs uptake. The P. palustris and S. americanum proved to be particularly strong accumulators of all K congeners from the soil. Some species that were measured, warrant further investigation, are the carnivorous plant Utricularia inflata (bladderwort) and the emergent macrophyte Juncus effusus. For U. inflata, the levels of (137)Cs, (238)Pu, and (239,240)Pu (which were 3922, 8399, and 803 Bq kg(-1), respectively) in the leaves were extremely high. The highest (137)Cs concentration from the study was measured in the J. effusus root (5721 Bq kg(-1)).
(137)Cs is one of the conservative tracers applied to the study of oceanic circulation processes on decadal time scales. To investigate the spatial distribution and the temporal variation of (137)Cs concentrations in surface seawater in the North Pacific Ocean after 1957, a technique for optimum interpolation (OI) was applied to understand the behaviour of (137)Cs that revealed the basin-scale circulation of (137)Cs in surface seawater in the North Pacific Ocean: (137)Cs deposited in the western North Pacific Ocean from global fallout (late 1950s and early 1960s) and from local fallout (transported from the Bikini and Enewetak Atolls during the late 1950s) was further transported eastward with the Kuroshio and North Pacific Currents within several years of deposition and was accumulated in the eastern North Pacific Ocean until 1967. Subsequently, (137)Cs concentrations in the eastern North Pacific Ocean decreased due to southward transport. Less radioactively contaminated seawater was also transported northward, upstream of the North Equatorial Current in the western North Pacific Ocean in the 1970s, indicating seawater re-circulation in the North Pacific Gyre.
Global nuclear weapons tests fallout of 137Cs in the northern hemisphere has been documented in the UNSCEAR (United Nations Scientific Committee on the Effect of Atomic Radiation) reports. However, many questions have arisen during the past three to four decades; e.g. the water column inventory of 137Cs in the North Pacific Ocean was two to three time higher than the cumulative decay corrected fallout at the same latitude as stated in the UNSCEAR reports. Here we show more precise spatial distribution of global 137Cs fallout primarily on the basis of global measurements in rain, seawater and soil, as data from 10 degrees x 10 degrees grids. A typical feature of geographical distribution is that two high global 137Cs fallout areas exist in the northern hemisphere, where the highest 137Cs fallout was observed in the globe. These areas correspond to crossovers of areas where larger precipitation amounts were expected and where higher stratosphere-troposphere exchange was expected. Our new estimate of 765 +/- 79 PBq as global 137Cs fallout for the northern hemisphere is 1.4 times higher than that of 545 PBq in the UNSCEAR reports.
We investigated spatial and temporal variations in (137)Cs concentrations in the surface waters of the global ocean for the period from 1957 to 2005 using the "HAM database - a global version". Based on the 0.5-y average value of (137)Cs concentrations in the surface water in each sea area, we classified the temporal variations into four types. (1) In the North Pacific Ocean where there was high fallout from atmospheric nuclear weapons tests, the rates of decrease in the (137)Cs concentrations changed over the five decades: the rate of decrease from the 1950s to the 1970s was much faster than that after the 1970s, and the (137)Cs concentrations were almost constant after the 1990s. Latitudinal differences in (137)Cs concentrations in the North Pacific Ocean became small with time. (2) In the equatorial Pacific and Indian Oceans, the (137)Cs concentrations varied within a constant range in the 1970s and 1980s, suggesting the advection of (137)Cs from areas of high global fallout in the mid-latitudes of the North Pacific Ocean. (3) In the eastern South Pacific and Atlantic Oceans (south of 40 degrees S), the concentrations decreased exponentially over the five decades. (4) In the Arctic and North Atlantic Oceans, including marginal seas, (137)Cs concentrations were strongly controlled by discharge from nuclear reprocessing plants after the late 1970s. The apparent half-residence times of (137)Cs in the surface waters of the global ocean from 1970 to 2005 ranged from 4.5 to 36.8 years. The apparent half-residence times were longer in the equatorial region and shorter in the higher latitudes. There was no notable difference between the latitudinal distributions of the apparent half-residence times in the Pacific and Indian Oceans. These results suggest that (137)Cs in the North Pacific Ocean is transported to the equatorial, South Pacific, and Indian Oceans by the oceanic circulation.
The depth distribution of plutonium, americium, and 137Cs originating from the 1986 accident at the Chernobyl Nuclear Power Plant (NPP) was investigated in several soil profiles in the vicinity from Belarus. The vertical migration of transuranic elements in soils typical of the 30 km relocation area around Chernobyl NPP was studied using inductively coupled plasma mass spectrometry (ICP-MS), alpha spectrometry, and gamma spectrometry. Transuranic concentrations in upper soil layers ranged from 6 x 10(-12) g g(-1) to 6 x 10(-10) g g(-1) for plutonium and from 1.8 x 10(-13) g g(-1) to 1.6 x 10(-11) g g(-1) for americium. These concentrations correspond to specific activities of (239+240)Pu of 24-2400 Bq kg(-1) and specific activity of 241Am of 23-2000 Bq kg(-1), respectively. Transuranics in turf-podzol soil migrate slowly to the deeper soil layers, thus, 80-95%, of radionuclide inventories were present in the 0-3 cm intervals of turf-podzol soils collected in 1994. In peat-marsh soil migration processes occur more rapidly than in turf-podzol and the maximum concentrations are found beneath the soil surface (down to 3-6 cm). The depth distributions of Pu and Am are essentially identical for a given soil profile. (239+240)Pu/137Cs and 241Am/137Cs activity ratios vary by up to a factor of 5 at some sites while smaller variations in these ratios were observed at a site close to Chernobyl, suggesting that 137Cs is dominantly particle associated close to Chernobyl but volatile species of 137Cs are of relatively greater importance at the distant sites.
The anthropogenic radionuclides, 90Sr and 137Cs, were measured in two marine algal species, wakame seaweed (Undaria pinnatifida) and edible kelp (Laminaria longissima), collected in four coastal areas of Japan during 1998-2008. Although 90Sr and 137Cs could be detected at all sampling sites, the concentrations of 90Sr and 137Cs were at low levels and those in some samples were below the detection limit. These low concentrations and the small variation of both concentrations and the 137Cs/90Sr activity ratio indicate that the source of 90Sr and 137Cs detected in this study originated from the global fallout deposition following atmospheric nuclear-bomb tests in the past. There were no significant differences in both concentrations of 90Sr and 137Cs in wakame seaweed among three sampling sites. Although wakame seaweed is extensively distributed in southern and central Japan, it does not occur in northern areas and so edible kelp was monitored. The concentrations of 90Sr and 137Cs in edible kelp were significantly different from those in wakame seaweed in some sampling sites. These differences could be due to the difference in the concentrations of 90Sr and 137Cs in the surrounding seawater or the difference in species. The combined data with data from the previous report and the preexisting database showed that wakame seaweed incorporated 137Cs through a different pathway from that of 90Sr. The combined data also suggested that wakame seaweed responded differently to the source of 137Cs.
Organic air particulate matter was analysed by applying the techniques of Py-GC-MS (pyrolysis-gas chromatography-mass spectrometry) and solid state 13C-NMR (nuclear magnetic resonance). Particles dislodged from air particulate filters and humic acid extracted from these filters were studied for structural components. The structural components of the air particles and extracted humic acid consisted of compounds originating from biomacromolecules, namely, lignin, carbohydrates, protein and lipids. The main components identified for each class included: (1) methoxyphenols originating from lignin; (2) furans, aldehydes and ketones from carbohydrates; (3) pyrrole, indoles from protein; and (4) many hydrocarbons from lipid structures. Single ion monitoring (SIM) and tetramethyl ammonium hydroxide (TMAH) methylation were utilised for detection of aliphatic hydrocarbons and acidic components, respectively. Hydrocarbons ranging from C9 to C28 were detected by SIM analysis, while aliphatic acids ranged from C9 to C18. The majority of components analysed directly in the air particles were similar to those from the humic acid extracts. Many of the structural components of air particles were typical of humic substances of soil and aqueous systems and these were attributed to both biogenic and anthropogenic sources.
In 13C cross-polarisation magic angle spinning (CPMAS) spectra of soil samples, the paramagnetic soil constituents partially discriminate against the signal intensity of the 13C atoms. The aim of the present study was to check to what extent this signal depression depends on the paramagnetic ion content and if it is selective for a certain kind of carbon species. The spectra of a variety of particle size fractions of five quite different soils were recorded. A procedure was developed to compare quantitatively the relative carbon content of the different spectra. It was found that iron ions differ in their efficiency to discriminate against the carbon signals. Nevertheless a strong linear correlation between the detectability of carbon and cube root(wt.%Fe) was observed for both the total signal and the signal of the different carbon species as well. This underlines that iron ions mainly influence the depression of the 13C signal in soil spectra. Furthermore we found, that for C: Fe ratios of 1.5 to 20 non-selective signal losses dominate. Despite a high percentage of non-detectable carbon (up to 90%), the 13C CPMAS spectra of our soil samples correctly reflect the relative composition of soil organic matter.