Efficacy of a Biomonitoring (Moss Bag) Technique for Determining Element Deposition Trends on a Mid-Range (375 Km) Scale

National networks detect multi-state trends in element deposition using direct measurement methods. Biomonitoring techniques have been used to examine deposition in local areas and around point sources. We sought to determine the efficacy of a moss bag technique to detect element deposition trends on a mid-range (state) scale, and to compare these results with those of the National Acid Deposition Program/National Trends Network (NADP/NTN, 1999). We sampled heavy metals, sulfur, and nitrogen deposition (21 elements) using mesh bags containing Sphagnum russowii at nine sites, over a 375 km transect crossing southern Wisconsin (upper Midwest, USA). We found statistically significant trends of decreasing deposition in a northwesterly direction for 13 elements: Al, B, Ca, Cd, Co, Cu, Cr, Fe, Mg, Mn, Ni, S, and Zn. Six of these have moderate to large changes in concentration (14–37%). The trends for Ca, Mg, and S are consistent with regional deposition patterns in 1998 isopleth maps from the NADP/NTN (1999) which are derived from a sampling array far less dense than the transect sites. This national network indicates that Ca and Mg increase to the southeast, beyond Wisconsin borders. The fact that the present study demonstrates strong correlations between both of these elements (Ca and Mg) and Al, B, Cr, Cu, Fe, Mn, Ni, and Zn (mean r for all correlations = 0.75, p < 0.02) implies that these correlated elements also increase to the southeast in neighboring states.     

Spatiotemporal distribution of airborne elements monitored with the moss bags technique in the Greater Thriasion Plain, Attica, Greece

The well-known moss bags technique was applied in the heavily polluted Thriasion Plain region, Attica, Greece, in order to study the spatiotemporal distribution, in the atmosphere, of the following 32 elements: Na, Al, Cl, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Zn, As, Se, Br, Sr, Mo, Sb, I, Ba, La, Ce, Sm, Tb, Dy, Yb, Hf, Ta, Hg, Th, and U. The moss bags were constituted of Sphagnum girgensohnii materials. The bags were exposed to ambient air in a network of 12 monitoring stations scattered throughout the monitoring area. In order to explore the temporal variation of the pollutants, four sets of moss bags were exposed for 3, 6, 9, and 12 months. Instrumental neutral activation analysis was used for the determinations of the elements. The data were analyzed using the Pearson correlations, the partial redundancy analysis, and the biplot statistical methods. Some pairs of elements were highly correlated indicating a probable common source of origin. The levels of the measured pollutants were unevenly distributed throughout the area and different pollutants exhibited different spatial patterns. In general, higher loads were observed in the stations close to and within the industrial zone. Most of the measured elements (e.g., Al, Ca, Ni, I, Zn, Cr, and As) exhibited a monotonic accumulation trend over time. Some elements exhibited different dynamics. The elements Mn, Mo, and Hg showed a decreasing trend, probably due to leaching and/or volatilization processes over time. Na and Br initially showed an increasing trend during the winter and early spring periods but decreased drastically during the late warm period. The results further suggest that the moss bags technique would be considered valuable for the majority of elements but should be used with caution in the cases of elements vulnerable to leaching and/or volatilization. It also suggests that the timing and the duration of the exposure of moss materials should be considered in the interpretation of the results.     

Uptake of metal ions in moss from artificial precipitation

Uptake in Hylocomium splendens and Sphagnum fuscum, of Zn, Cu, Cd, and Pb from artificial solutions of precipitation at ambient concentration levels was investigated. The primary objective was to study to what extent major cations and possibility anions in the precipitation might affect the uptake by competition or possibly by complexing reactions. In addition the effect on metal uptake of pH and temperature was studied. The uptake of Zn and partly Cu was lower from precipitation with a high content of seasalt. With increasing metal concentration an increasing amount of Zn and Cu accumulated in the moss. These observations suggest that cations in the precipitation such as Na⁺ and Mg²⁺ may affect the uptake by competition. Possibly also Cl^- may interfere by complexing reactions. Uptake of Zn and Cd was pH dependent. The uptake of all four metals increased with temperature. The results from this work appear to be significant with respect to the interpreation of data from atmospheric deposition surveys based on moss analysis.     

Assessment of Atmospheric Deposition of Heavy Metals and Other Elements in Belgrade Using the Moss Biomonitoring Technique and Neutron Activation Analysis

This study aimed at assessing atmospheric deposition of heavy metals and other elements using the moss genera Brachythecium sp. (B. rutabulum and B. salebrosum) and Eurhynchium sp. (E. hians and E. striatum) collected in autumn 2004 in the urban area of Belgrade. The concentrations of 36 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Mo, Sb, I, Cs, Ba, La, Ce, Sm, Tb, Dy, Hf, Ta, W, Hg, Th, U) were determined in moss and local topsoil samples by instrumental neutron activation analysis. The concentration of elements in moss positively correlated to those obtained for topsoil. High enrichment factors for As, Zn, Mo, Br, Sb, Se, Hg and Cl, calculated to continental crust composition, gave an evidence for anthropogenic impact on urban area, mainly due to intensive vehicular traffic and fossil fuel combustion. The concentration of elements in moss, characteristic for fossil fuel combustion, obtained in this study were substantially lower than in the previous investigation (2000) conducted in the area of Belgrade. The level of concentrations for V, Cr, Ni, and As in moss from this study correlated to those measured for neighboring countries, and were several times higher than the base-level data from low polluted areas. The level of accumulated elements in both investigated moss genera were similar and all studied species could be combined for biomonitoring purposes in urban areas.     

A Comparison Between Two Moss Species Used as Transplants for Airborne Trace Element Biomonitoring in NE Italy

Transplants of the mosses Hypnum cupressiforme and Pseudoscleropodium purum used as active biomonitors of airborne trace elements were compared in a survey carried out at Trieste (NE Italy). Twelve elements were considered: Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Ti, V, Zn. Water-washed materials of H. cupressiforme and P. purum, collected in a remote area to prepare transplants, showed comparable content of all elements, excluding Pb. Transplants of P. purum showed a significantly higher accumulation of Al, Fe, Pb and Ti; higher levels of Cu and V were accumulated in H. cupressiforme. Losses of some elements occurred in some samples of both species; the most consistent losses regarded Cr and Mn. Accumulation data of Al, As, Cd, Hg, Zn found in the two transplanted sets were not correlated. Differences in element uptake in the two mosses are likely to depend mainly on morphology, and probably on the different forms of emission and deposition types of the elements. The two mosses showed an overall accordance in discriminating sites highly and scarcely affected by trace element depositions, although they accumulated some elements, in particular Hg and Zn, in different ways. P. purum proved to be a better accumulator than H. cupressiforme, showing similar or higher accumulation and lower loss of almost all elements, especially those related to particulate, dry depositions; H. cupressiforme could be effective in detecting large-scale patterns, related to wet depositions. These results indicate that these mosses cannot be used interchangeably for monitoring particular elements, and are able to provide complementary information on different, local and long-range deposition patterns.     

Assessment of the impact of petroleum and petrochemical industries to the surrounding areas in Malaysia using mosses as bioindicator supported by multivariate analysis

Biomonitoring of multi-element atmospheric deposition using terrestrial moss is a well-established technique in Europe. Although the technique is widely known, there were very limited records of using this technique to study atmospheric air pollution in Malaysia. In this present study, the deposition of 11 trace metals surrounding the main petroleum refinery plant in Kerteh Terengganu (eastern part of peninsular Malaysia) has been evaluated using two local moss species, namely Hypnum plumaeforme and Taxithelium instratum as bioindicators. The study was also done by means of observing whether these metals are attributed to work related to oil exploration in this area. The moss samples have been collected at 30 sampling stations in the vicinity of the petrochemical industrial area covering up to 15 km to the south, north, and west in radius. The contents of heavy metal in moss samples were analyzed by energy dispersive x-ray fluorescence technique. Distribution of heavy metal content in all mosses is portrayed using Surfer software. Areas of the highest level of contaminations are highlighted. The results obtained using the principal components analysis revealed that the elements can be grouped into three different components that indirectly reflected three different sources namely anthropogenic factor, vegetation factor, and natural sources (soil dust or substrate) factor. Heavy metals deposited mostly in the distance after 9 km onward to the western part (the average direction of wind blow). V, Cr, Cu, and Hg are believed to have originated from local petrochemical-based industries operated around petroleum industrial area.     

Analysis of selected biomonitors to evaluate the suitability for their complementary use in monitoring trace element atmospheric deposition

The biomonitoring properties of oak tree bark compared with the epiphytic moss Hypnum cupressiforme and the influence of the tree bark, as its growth substrate, on the content of heavy metals in moss were investigated. Samples of the epiphytic moss H. cupressiforme and oak tree bark (Quercus spp.) were collected in Eastern Romania at a total of 44 sampling sites. Parallel moss and bark samples were collected from the same sides of the trunk circumference. V, Cr, Ni, Cu, Zn, As, Mo, Cd, In, Tl, Sn, Pb, and Bi were determined by ICP-MS. Principal component analysis was used to identify possible sources of metals in bark and moss. Six factors explaining 87 % of the total variance in the data set were chosen. The main factors represent long-range atmospheric transport of elements (Zn, Cd, (Pb), Bi, (Mo), (Tl)), local emissions from industrial sources (As, Cr, Ni, V), road traffic (Pb, Zn) and agricultural activities (Cu, (Zn)). The element concentrations in moss and bark samples are of the same order of magnitude. For almost all the elements, higher concentrations were obtained in moss. Significant correlations between concentrations in moss and bark samples were obtained for 7 of the 13 elements: V, Ni, Cu, Zn, Cd, In, and Bi, all typical anthropogenic pollutants. The use of tree bark for monitoring purposes might be an alternative in areas where there is a scarcity of mosses.     

Comparison of two metal surveys by moss Tortula ruralis in Budapest, Hungary

Moss transplants of Tortula ruralis were used as active biomonitoring organisms as part of a monitoring study to assess the metals (Al, Cd, Cu, Cr, Fe, Ni, Pb, V and Zn) associated with ambient particles on mosses in Budapest, the capital town of Hungary. The moss samples were collected in a nature conservation area from a semi-arid sand grassland (Festucetum vaginatae danubiale), less than 1 month before transplantation. Moss cushions were exposed to pollution in Budapest during October–November 1993 and February–March 1994. In the study area, 16 sites were marked out as measuring sites, in accordance with the structure of the city. A similar stand was established in the Botanical Gardens of the Szent István University in Gödöll? as a control site. ICP-AES analysis of moss for metals showed the ability of Tortula ruralis to accumulate the metals under study. Control site showed lower impact in comparison to the other sites.     

Moss interspecies comparisons in trace element concentrations

Within the framework of a European-scaled moss survey, various moss species were sampled throughout The Netherlands [NL], Germany [D], and Switserland [CH], and used in moss interspecies comparisons of elemental concentrations. Moss species considered were Pleurozium schreberi [NL,D,CH], Brachythecium rutabulum [NL], Hypnum cupressiforme [D,CH], Hylocomium splendens [D,CH], and Scleropodium purum [D]. Element analysis was carried out directly (The Netherlands, Instrumental Neutron Activation Analysis: As, Br, Ce, Cr, Cs, Fe, La, Mn, Na, Rb, Sc, Se, Sm, Th, Ti, V and Zn), or after sample digestion (The Netherlands, ICP-MS: Pb, Germany, AAS/ICP-AES: Cd, Cr, Cu, Fe, Ni, Pb, Ti, V, and Zn; Switzerland, ICP-AES/ICP-MS: Co, V, and Zn).Local variations (=within sampling sites) in element concentrations were estimated, based upon in-site multiple sampling and analysis of Pleurozium schreberi species in The Netherlands. Element concentrations in moss species were compared in linear correlations, both in unweighted and weighted fits, with weighing factors based on the local variation data. Weighted fits were shown to generally improve the calibration characteristics, as tracked by X ² calculations.The calibration data suggest the presence of previously unnoticed outliers in element concentrations. The absence of further information, however, may prescribe the use of all data in comparison procedures. These results indicate that interlaboratory analysis of replicate samples and the use of dedicated certified reference materials may help solving problems in the analysis of the sample series.For several of the considered interspecies comparisons, weighted calibrations could be based on significant correlations (P=0.05). Actual use, however, will remain arbitrarily decided upon, and may be based on decisions as to what to accept with respect to the levels of uncertainty in the calibration parameters. Furthermore, the use of calibrations in extrapolation modes is greatly restricted by the necessary reservations in geographically larger-scaled applications.     

Heavy Metals Content in N. OleanderLeaves As Urban Pollution Assessment

Nerium oleanderL. (Oleander) leaves grown in Palermo city (Sicily, Italy) were collected from six sampling sites representing either areas of high traff{i}c and urbanisation density or areas far away from traffic (e.g. city gardens). Concentration of Al, Ba, Cr, Cu, Fe, Pb, Mg, Mn, and Zn were determined in leaf samples during two years. Multivariate analysis classified the sampling sites in four groups based on the metal content in vegetal leaves in agreement with traffic and human activity site. Many elements studied (Al, Ba, Fe, Mn Mg) arise from the soil composition and others such as Cr, Cu, Pb and Zn as pollutant of the soil. On the other hand, about 30% of Al, Fe Cr, Cu and Pb originate from aerial deposition on leaves. Although the results presented should be handled with caution N. oleandercan be considered as a means of assessing dust contamination in the urban environment.     

Atmospheric background trace elements deposition in Tierra del Fuego region (Patagonia,Argentina), using transplanted <Emphasis Type="Italic">Usnea barbata</Emphasis> lichens

Lichen, Usnea barbata, transplants taken from Tierra del Fuego (south Patagonia, Argentina) were tested as potential biomonitors of atmospheric airborne deposition in an apparently pristine environment. In 2005, lichens were sampled in a reference site (n = 31) and transplanted in the northern Region of Tierra del Fuego. After, respectively, 1 month and 1 year of exposure, we collected them. The aim of the study was to determine the bioaccumulation of 26 elements in order to evaluate the background levels in the selected area. Samples were analyzed by the sector field inductively coupled plasma mass spectrometry. Discriminant analysis on principal component analysis factors was applied in order to explore the relationship among the different elements as far as time and spatial variation in transplants regards. The analysis was tested by Monte Carlo test based on 999 replicates. The most important contamination source resulted to be the atmospheric soil particle deposition. Furthermore, the results were compared with those obtained from the lichens collected in central and southern Tierra del Fuego. This study confirms the ability of U. barbata to reflect the background levels of the 26 elements in that environment. Compared with other background sites in the world, we did confirm that Tierra del Fuego lichens have a low content of the studied elements. Tierra del Fuego turned out not to be a pristine environment as supposed, but it can be considered as a reference basal ecosystem for useful comparisons among different geographical areas. These findings can be very relevant and useful for environmental conservation programs.     

Inter-Laboratory Comparison of No2 and SO2 Generated by Dynamic Dilution System Under Laboratory Conditions: A Technical Discussion

A workshop on analytical quality control (AQC) of ambient air quality measurement methods for nitrogen dioxide (NO₂) and sulphur dioxide (SO₂) was conducted by Central Pollution Control Board (CPCB) for officials involved in National Ambient Air Quality Monitoring (NAAQM) in India. Concentrations of NO₂ and SO₂ were generated by dynamic dilution system under laboratory conditions at low and high levels and measured using static dilution system and wet chemical methods laid down by CPCB under section 16(2)(h) of the air act 1981. CPCB provided the measured values as reference values for comparing the means obtained by the officials participated from thirteen organizations. A tolerance limit of ±15% of the reference values was specified to accept the results. Generated concentrations, which were unknown to the participants, were measured using gaseous sampling assembly (Envirotech APM 411, New Delhi, India), and wet chemical methods laid down by CPCB i.e. the same methodology which is used by the organizations to generate the data of NO₂ and SO₂ in ambient air. Simultaneously, concentrations were checked by CPCB using automatic analyzers as a check on reference concentration. It is observed that results of automatic analyzers for NO₂ and SO₂ were within a tolerance of ±5% with %RSD below 3. On the other hand, results of most of the participants showed variability in the measurements with %RSD ranging between ±0.8 and ±88.6 and exceedences of means from the tolerance limit with bias ranging between 1.4 and −59%. To check the cause of high variability in the measurements obtained under identical conditions, duplicate sampling was performed by one of the participants for SO₂ at low concentration level. In this study, results of wet chemical methods, automatic analyzers and results of duplicate sampling are analysed statistically to assess the cause of high variability in the measurements. Analysis of t-test and analysis of variance (ANOVA) showed highly significant results for NO₂ and SO₂ at high concentration levels (α 0.05) and for SO₂ at both the levels (α 0.01) respectively indicating some bias is existing either in the sampling or in analytical technique. Duplicate sampling performed to check precision in parallel measurements showed high %RSD indicating the presence of systematic error in sampling technique as the same calibration factor (CF) was used to measure the concentration of duplicate samples. Statistical analysis of flow rates of duplicate sampling showed that the sampling assembly could not maintain the constant flow rate within the ±10% with that measured at the start of the sampling. This resulted in high %RSD and deviation from the reference values for the results of most of the participants, even after accepting ±15% tolerance limit. There is a need to improve and evaluate this gaseous sample collection device under laboratory conditions to generate reliable database of NO₂ and SO₂ in ambient air.     

Identifying the origin of atmospheric inputs of trace elements in the Prades Mountains (Catalonia) with bryophytes, lichens, and soil monitoring

The biomonitors Hypnum cupressiforme and Xanthoria parietina were used to assess the deposition of trace elements and their possible origin in the Prades Mountains, a protected Mediterranean forest area of NE Spain with several pollution sources nearby. Al, As, Cd, Co, Cu, Cr, Ni, Pb, Sb, Ti, V, and Zn were determined in 16 locations within this protected area. Soil trace element concentrations were also ascertained to calculate enrichment factors (EF) and use them to distinguish airborne from soilborne trace element inputs. In addition, lichen richness was measured to further assess atmospheric pollution. EF demonstrated to be useful not only for the moss but also for the lichen. Cd, Cr, Cu, Ni, and Zn presented values higher than three in both biomonitors. These trace elements were also the main ones emitted by the potential sources of pollutants. The distance between sampling locations and potential pollution sources was correlated with the concentrations of Cu, Sb, and Zn in the moss and with Cr, Ni, and Sb in the lichen. Lichen richness was negatively correlated with lichen Cu, Pb, and V concentrations on dry weight basis. The study reflected the remarkable influence that the pollution sources have on the presence of trace elements and on lichen species community composition in this natural area. The study highlights the value of combining the use of biomonitors, enrichment factors, and lichen diversity for pollution assessment to reach a better overview of both trace elements’ impact and the localization of their sources.     

The Use of Mytilus Galloprovincialis Acetylcholinesterase and Glutathione S-Transferases Activities as Biomarkers of Environmental Contamination Along the Northwest Portuguese Coast

With the aim of using Mytilus galloprovincialis acetylcholinesterase (AChE) and glutathione S-transferases (GST) activities as biomarkers of environmental contamination in risk assessment studies along the northwest Portuguese coast, the objective of this study was to provide background information related to: (1) baseline values of these enzymatic activities both in reference and contaminated areas and their responsiveness as indicators of exposure to environmental contaminants; (2) the importance of seasonal variations of such biomarkers in M. galloprovincialis along this area. For this, the activity of these enzymes was seasonally determined in mussels collected from four sites, including a reference and three stations with different contamination sources along the referred area. Statistically significant differences on both enzymatic activities were found among the four sampling stations, at the four sampling periods. In comparison to the reference station, lower AChE and higher GST activity values were found in mussels collected in stations potentially contaminated by pesticides and domestic/industrial effluents and in mussels collected in the vicinity of an oil refinery and an industrial/mercantile harbour, respectively. The results obtained in this work highlighted the potential suitability of these biomarkers to be used as components of environmental monitoring programs in risk assessment studies along the northwest Portuguese coast. Since a seasonal variation in both enzymatic activities was found, the possible implications of such variability in the use of these enzymes as environmental biomarkers are also discussed.     

Trace Element Concentrations and Bioindicator Responses in Tree Swallows from Northwestern Minnesota

Extremely high concentrations of cadmium (3.5 μg/g dry wgt.) and elevated concentrations of chromium (>10 μg/g dry wgt.) and mercury (1.6 μg/g dry wgt.) were reported in waterbird tissues at Agassiz National Wildlife Refuge in northwestern Minnesota in 1994. Tree swallows (Tachycineta bicolor) were studied during 1998–2001 at three drainages into the Refuge, two pools on the Refuge, and at a nearby reference location to document whether high levels of contaminants were still present, and if so to quantify the source and severity of the contamination. Trace elements were measured in tree swallow eggs, livers, and diet. Reproductive success and bioindicator responses were monitored. In 2000, water was drawn down on Agassiz Pool, one of the main pools on the Refuge. This presented an opportunity to evaluate the response of trace element concentrations in the diet and tissues of tree swallows after reflooding. High concentrations of trace elements were not detected in swallow tissues, nor were there differences among locations. Less than 20% of swallow samples had detectable concentrations of cadmium or chromium. Mercury concentrations were low and averaged <0.25 μg/g dry wgt. in swallow tissues. Trace elements, including mercury, did not increase in tree swallows following the 2000 drawdown at Agassiz Pool. Hatching success and survival of nestlings to 12 days-of-age for tree swallows on the Refuge were similar to the national average and consistent with background trace element concentrations. Bioindicator measurements were within the normal ranges as well.     

A survey of Pb,Cu, Zn,Cd, Cr,As, and Se in earthworms and soil from diverse sites

Earthworms and soils were collected from 20 diverse sites in Maryland, Pennsylvania, and Virginia, and were analyzed for Pb, Cu, Zn, Cd, Cr, As, and Se. Correlation coefficients relating concentrations of the elements in earthworms to concentrations in soil were low (–0.20<r<+0.57). Species differences and ecological variables contributed to the variability in concentrations of these elements in earthworms. The maximum concentrations of Pb (2100 ppm), Zn (1600 ppm), Cd (23 ppm) and Se (7.6 ppm) detected in earthworms were in the range reported to be toxic to animals fed diets containing these elements; however, even in the absence of any environmental contamination, some species of earthworms may contain high concentrations of Pb, Zn, and Se. Earthworms of the genus Eisenoides, for example, were exceptional in their ability to concentrate Pb. When earthworms are used as indicators of environmental contamination, it is important to identify the species, to report the soil characteristics, and to collect similar earthworms from very similar but uncontaminated soil.     

Hydrocarbon Utilization in Yeast Isolates Found to Grow in Association with Petroleum in a Polluted Ultisol of Midwestern Nigeria

The population counts of hydrocarbon-utilising yeasts weremonitored at six sampling stations in the Benin City municipalarea over a four-week period. Although the population countswere relatively constant in each locality, the highest countsoccurred in areas heavily polluted by domestic and industrialeffluents. A total of thirty-five hydrocarbon-degrading yeastswere isolated from soil at the sampling stations usingn-hexadecane as sole carbon source. The isolates were identifiedas belonging to the genera Candida (27 strains), Endomycopsis (4 strains). All the organisms grew on long-chainn-alkane, kerosene, diesel oil and crude oil but failed to growon short-chain n-alkane, aromatic and alicyclic hydrocarbons.Measurement of growth attributes of the isolates usingn-hexadecane, diesel oil and crude oil as substrates showed thatthe Candida species were better utilizers of hydrocarbonsubstrates relative to Endomycopsis and Schizosaccharomyces species.     

Measures of flow variability for great lakes tributaries

Design of monitoring programs for load estimation is often hampered by the lack of existing chemical data from which to determine patterns of flux variance, which determine the sampling program requirements when loads are to be calculated using flux-dependent models like the Beale Ratio Estimator. In contrast, detailed flow data are generally available for the important tributaries. For pollutants from non-point sources there is often a correlation between flow and pollutant flux. Thus, measures of flow variability might be calibrated to flux variability for well-known watersheds, after which flow variability could be used as a proxy for flux variability to estimate sampling needs for tributaries for which adequate chemical observations are lacking.Three types of measures of flow variability were explored: ratio measures, which are of the form q _x/q_y, where q _xis the flow corresponding to the percentile x, and y=100–x; spread measures, of the form (q _x–q_y)/q_m, where q _mis the median flow; and the coefficient of variation of the logs of flows. In the latter, flows are log transformed because flow distributions are often approximately log-normal. Three ratio measures were evaluated, based on the percentiles (10,90), (20,80), and (25,75). The analogous spread measures were also evaluated; the spread measure based on percentiles (25,75) is derived from the commonly used fourth spread of non-parametric statistics. The ratio measures and the spread measures are scale independent, and thus are measures only of the shape of the distribution. The coefficient of variation is also scale independent, but in log space.Values of these measures of flow variability for 120 Great Lakes tributaries are highly intercorrelated, although the relationship is often non-linear. The coefficient of variation of the log of the flows is also well correlated with the coefficient of variation of fluxes of suspended solids, total phosphorus, and chloride, for a smaller set of rivers where the existence of abundant chemical data allows comparison.Tributaries with abnormal distributions often show up as outliers when one measure of flow variability is plotted against another. Several examples are discussed.     

Biomonitoring for exposure to multiple trace elements via analysis of urine from participants in the study of metals and assisted reproductive technologies (SMART)

Humans are exposed to concentrations of multiple trace elements through a variety of background sources; many are suspected reproductive toxicants. Prior to investigating associations between trace elements and human reproductive health, potential biomarkers of exposure should be characterized by sources of variability in the population at risk. Factors influencing elemental exposure should also be identified to ensure their consideration as potential confounding variables. The principal aim of this study is to characterize sources of variability for 19 trace elements measured in urine specimens collected from 55 women and 36 male partners completing a 1st cycle of in vitro fertilization (IVF). Urine specimens were analyzed using a biomonitoring method based on inductively coupled plasma-mass spectrometry (ICP-MS). Randomly selected urine specimens (～6%) were analyzed in duplicate, and these data were used to characterize sources of variability. Nine trace elements including As, Ba, Cd, Cs, Co, Cu, Mn, Mo, and Zn, were quantified in most specimens, indicating their utility in future epidemiologic studies of trace elements exposure and IVF outcomes. With few exceptions, normalizing urine using the traditional creatinine-correction procedure, or an alternative approach based on a linear regression model, increased residual variability only slightly. Sex and race appear to be important factors to consider in epidemiologic studies conducted in this population. Urine concentrations for most elements are similar to those reported in the 2005-2006 National Health and Nutrition Examination Survey (NHANES); however, differences in others may indicate regional trends or a unique exposure history for this infertile study population.