Assigning concentration values for dioxin and furan congeners in human serum when measurements are below limits of detection: an observational approach

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in dietary sources for humans have been declining over the previous two decades. These declines have been accompanied by decreases in concentrations of these compounds in humans, as evidenced by measurements in blood and milk. Because of the decreasing concentrations of PCDD/PCDFs in the environment and in humans, measuring PCDD/PCDF congeners in humans has become increasingly difficult, despite advances in analytic methods. An observational approach was recently described to address the quandary of non-detectable results in determining toxic equivalents. This approach, called the congener ratio approach, is specifically for cases where concentrations of 2,3,7,8-TCDD (TCDD) are below the limit of detection (LOD), and where concentrations of 1,2,3,7,8-pentachlorodibenzo-p-dioxin (PeCDD) are equal to or above the LOD. Development of this approach relied on evaluating data on measured concentrations of TCDD and PeCDD in human serum from the general population. The congener ratio approach for TCDD and PeCDD was based on the concentration of TCDD being approximately 40% that of PeCDD in serum from the general population. Additional analyses presented here reveal that when concentrations of both congeners are above the LOD, the data appear to generally support the congener ratio approach for TCDD and PeCDD, with the caveat that gender may affect the ratio. However, the TCDD/PeCDD relation is less clear when TCDD is less than the LOD; in this situation, the relation overpredicts levels of TCDD approximately 80% of the time for the 2001-2002 NHANES database. Using the congener ratio approach for other PCDD/PCDF congeners requires assessing the correlation and the frequency of detection for both TCDD and PeCDD.     

Calculation of serum "total lipid" concentrations for the adjustment of persistent organohalogen toxicant measurements in human samples

Persistent organohalogen toxicants such as 2,3,7,8-tetrachlorodibenzo-p-dioxin or polychlorinated biphenyls measured in human serum are often expressed on a lipid weight basis, most commonly by dividing the toxicants' concentration by the weight of total lipids in the sample. Therefore, the manner in which this lipid adjustment is calculated may influence the final reported result. Gravimetric total lipid assays have been used, but they are time-consuming and sometimes may be ill-defined. Consequently, alternative methods using enzymatic assays have been developed based on summing the individual lipid species measured. Recent reports, however, have suggested that significantly different total lipid results may be obtained when using alternative formulae in a summation approach. In this report, we summarize the results obtained from lipid measurements of nearly 900 samples made as part of a study of a group of older American men (mean age 62 years), and we compare our total lipid estimates obtained by using both our standard and "short" formula (the latter based on total cholesterol and triglycerides only) with results obtained using the recently proposed alternative formulae. Our findings indicate that both our long and short formulae provide similar estimates of serum total lipid concentrations, and that differences observed in lipid estimates when using the newer alternative summation methods may reflect differences in how the term "total lipid" is defined, especially with regard to the need to include the contribution of the weight of the cholesterol ester fatty acids in the calculation.     

The use of 'exotic' framework structures in waste management

The use of porous framework materials in waste management applications has the potential to be a powerful tool in toxic metal remediation. The properties that these materials possess, including high surface area and ion-exchange capacity, are theoretically valuable. Furthermore, the flexibility of many of these frameworks allows the potential for immobilisation of waste materials with the framework of the material, in addition to the traditional capture in the pore structure. However, for either of these routes to be useful for waste management purposes, these structures must also be stable in any proposed storage media. This study examines the stability of a range of porous materials whose frameworks are made out of zinc and arsenic, both considered toxic minesite wastes, when exposed to aqueous media. The three frameworks examined (sodalite analogue Na(6)(H(2)O)(8)(ZnAsO(4))(6), open framework K(3)Zn(4)O(AsO(4))(3).3.5H(2)O, and an ABW type framework NH(4)ZnAsO(4)) all have similar hydrothermal synthetic routes and bulk framework compositions, but differ in counter ion used, pore size and complexity of structure. The phases were examined before and after storage in an aqueous environment, and their crystallinity and leaching were determined. All phases prepared were found to be extremely unstable outside their original synthetic environment, and very soluble when exposed to water, calling into question their practical use in any environment.     

Long-term changes in fish mercury levels in the historically impacted English-Wabigoon River system (Canada)

The English-Wabigoon River system in Northwestern Ontario, Canada, was one of the most heavily mercury-contaminated waterways in the world due to historical discharges in the 1960s from a chlor-alkali plant. This study examines long-term (1970-2010) monitoring data to assess temporal trends in mercury contamination in Walleye, Northern Pike and Lake Whitefish, three species important for sport and subsistence fishing in this region, using dynamic linear modeling and piecewise regression. For all lakes and species, there is a significant decline (36-94%) in mercury concentrations through time; however, there is evidence that this decline is either slowing down or levelling off. Concentrations in the English-Wabigoon fish are elevated, and may still present a potential health risk to humans consuming fish from this system. Various biotic and abiotic factors are examined as possible explanations to slowing rates of decline in mercury concentrations observed in the mid-1980s.     

Spatial and seasonal patterns in water quality in an embayment-mainstem reach of the tidal freshwater Potomac River, USA: a multiyear study

Spatial and temporal patterns in water quality were studied for seven years within an embayment-river mainstem area of the tidal freshwater Potomac River. The purpose of this paper is to determine the important components of spatial and temporal variation in water quality in this study area to facilitate an understanding of management impacts and allow the most effective use of future monitoring resources. The study area received treated sewage effluent and freshwater inflow from direct tributary inputs into the shallow embayment as well as upriver sources in the mainstem. Depth variations were determined to be detectable, but minimal due mainly to the influence of tidal mixing. Results of principal component analysis of two independent water quality datasets revealed clear spatial and seasonal patterns. Interannual variation was generally minimal despite substantial variations in tributary and mainstem discharge among years. Since both spatial and seasonal components were important, data were segmented by season to best determine the spatial pattern. A clear difference was found between a set of stations located within one embayment (Gunston Cove) and a second set in the nearby Potomac mainstem. Parameters most highly correlated with differences were those typically associated with higher densities of phytoplankton: chlorophyll a, photosynthetic rate, pH, dissolved oxygen, BOD, total phosphorus and Secchi depth. These differences and their consistency indicated two distinct water masses: one in the cove harboring higher algal density and activity and a second in the river with lower phytoplankton activity. A second embayment not receiving sewage effluent generally had an intermediate position. While this was the most consistent spatial pattern, there were two others of a secondary nature. Stations closer to the effluent inputs in the embayment sometimes grouped separately due to elevated ammonia and chloride. Stations closer to tributary inflows into the embayment sometimes grouped separately due to dilution with freshwater runoff. Segmenting the datasets by spatial region resulted in a clarification of seasonal patterns with similar factors relating to algal activity being the major correlates of the seasonal pattern. A basic seasonal pattern of lower scores in the spring increasing steadily to a peak in July and August followed by a steady decline through the fall was observed in the cove. In the river, the pattern of increases tended to be delayed slightly in the spring. Results indicate that the study area can be effectively monitored with fewer study sites provided that at least one is located in each of the spatial regions.     

Equivalency of a personal dust monitor to the current United States coal mine respirable dust sampler

The United States National Institute for Occupational Safety and Health, through an informal partnership with industry, labor, and the United States Mine Safety and Health Administration, has developed and tested a new instrument known as the Personal Dust Monitor (PDM). The new dust monitor is an integral part of the cap lamp that coal miners normally carry to work and provides continuous information about the concentration of respirable coal mine dust within the breathing zone of that individual. Previous laboratory testing demonstrated that there is a 95% confidence that greater than 95% of individual PDM measurements fall within +/-25% of reference measurements. The work presented in this paper focuses on the relationship between the PDM and respirable dust concentrations currently measured by a coal mine dust personal sampler unit utilizing a 10 mm Dorr-Oliver nylon cyclone. The United Kingdom Mining Research Establishment instrument, used as the basis for coal mine respirable dust standards, had been designed specifically to match the United Kingdom British Medical Research Council (BMRC) criterion. The personal sampler is used with a 1.38 multiplier to convert readings to the BMRC criterion. A stratified random sampling design incorporating a proportionate allocation strategy was used to select a sample of mechanized mining units representative of all US underground coal mines. A sample of 180 mechanized mining units was chosen, representing approximately 20% of the mechanized mining units in production at the time the sample was selected. A total of 129 valid PDM/personal sampler dust sample sets were obtained. A weighted linear regression analysis of this data base shows that, in comparison with the personal sampler, the PDM requires a mass equivalency conversion multiplier of 1.05 [95% C.I.=(1.03, 1.08)] when the small intercept term is removed from the analysis. Removal of the intercept term results in a personal sampler-equivalent concentration increase of 2.9% at a PDM measurement of 2.0 mg m(-3).     

Comparison of DNA extraction methodologies used for assessing fungal diversity via ITS sequencing

Traditional methods of assessing fungal exposure have been confounded by a number of limiting variables. The recent utilization of molecular methods such as internal transcribed spacer (ITS) sequencing of ribosomal RNA genes has provided improved insight into the diversity of fungal bioaerosols in indoor, outdoor and occupational environments. However, ITS analyses may also be confounded by a number of methodological limitations. In this study, we have optimized this technology for use in occupational or environmental studies. Three commonly used DNA extraction methodologies (UltraClean Soil kit, High Pure PCR Template kit, and EluQuik/DNeasy kit) were compared in terms of sensitivity and susceptibility to PCR inhibitors in dust for three common fungal bioaerosols, Aspergillus versicolor, Rhizopus microsporus and Wallemia sebi. Environmental dust samples were then studied using each extraction methodology and results were compared to viable culture data. The extraction methods differed in terms of their ability to efficiently extract DNA from particular species of fungi (e.g. Aspergillus versicolor). In addition, the ability to remove PCR inhibitors from dust samples was most effective using the soil DNA extraction kit. The species composition varied greatly between ITS clone libraries generated with the different DNA extraction kits. However, compared to viable culture data, ITS clone libraries included additional fungal species that are incapable of growth on solid culture medium. Collectively, our data indicated that DNA extraction methodologies used in ITS sequencing studies of occupational or environmental dust samples can greatly influence the fungal species that are detected.     

Five year-round forage systems in a dairy effluent sprayfield: phosphorus removal

In northern Florida, forages are grown in dairy effluent sprayfields to recover excess P. Our purpose was to evaluate five year-round forage systems for their capacity to remove P from a dairy sprayfield. The soil is a Kershaw sand (thermic, uncoated Typic Quartzipsamment). Systems included bermudagrass (Cynodon spp.)-rye (Secale cereale L.) (BR), perennial peanut (Arachis glabrata Benth.)-rye (PR), corn (Zea mays L.)-forage sorghum [Sorghum bicolor (L.) Moench]-rye (CSR), corn-bermudagrass-rye (CBR), and corn-perennial peanut-rye (CPR). Forages were grown for five 12-mo cycles. Effluent P rates were 80, 120, and 165 kg ha-1 cycle-1. The 5-cycle P removal was 67 kg ha-1 cycle-1 for BR, 54 kg ha-1 for CBR, 52 kg for CSR, 45 kg for PR, and 43 for CPR. Removal of P by winter rye was low. There were differences in system rankings among cycles primarily due to changes in the performance of perennial forages. In the first two cycles, BR had the greatest P removal (91 kg ha-1 cycle-1) due to high bermudagrass yield and P concentration. In the first cycle, P removal was lowest for PR (36 kg ha-1) because perennial peanut was slow to establish. In later cycles, P removal for BR declined because bermudagrass yield and P concentration declined. It increased for PR because peanut yield increased. The yield of corn in CBR, CPR, and CSR was consistently high but P concentration was modest (avg. 2.2 g kg-1). Sorghum produced moderate but stable yield and had low P levels (avg. 1.8 g kg-1). Effluent rate marginally affected the performance of most grasses. For P recovery in dairy sprayfields in northern Florida, the best warm-season forage would likely be a high yielding, persistent bermudagrass.     

Phosphorus and other soil components in a dairy effluent sprayfield within the central Florida Ridge

There is concern that P from dairy effluent sprayfields will leach into groundwater beneath Suwannee River basins in northern Florida. Our purpose was to describe the effects of dairy effluent irrigation on the movement of soil P and other nutrients within the upper soil profile of a sprayfield over three 12-mo cycles (April 1998-March 2001). Effluent P rates of 70, 110, and 165 kg ha(-1) cycle(-1) were applied to forages that were grown year-round. The soil is a deep, excessively drained sand (thermic, uncoated Typic Quartzipsamment). Mean P concentration in soil water below the rooting zone (152-cm depth) was < or = 0.1 mg L(-1) during 11 3-mo periods. Mehlich-1-extractable (M1) P, Al, and Ca in the topsoil increased over time but did not change in subsoil depths of 25 to 51, 51 to 71, 71 to 97, and 97 to 122 cm. Topsoil Ca increased as effluent rate increased. High Ca levels were found in dairy effluent (avg.: 305 mg L(-1)) and supplemental irrigation water (avg.: 145 mg L(-1)) which likely played a role in retaining P in the topsoil. An effect of effluent rate on P and Al concentrations in the topsoil was not detected, probably due to large and variable quantities present at project initiation. The P retention capacity (i.e., Al plus Fe) increased in the topsoil because Al increased. Dairy effluent contained Al (avg.: 31 mg L(-1)). Phosphorus saturation ratio (PSR) increased over time in the topsoil but not in subsoil layers. Regardless of effluent rate, the P retention capacity and PSR of subsoil, which contained 119 to 229 mg kg(-1) of Al, should be taken into account when assessing the risk of P moving below the rooting zone of most forage crops.     

镉和铬对多毛类环节动物小头虫两个种群的效应

本文系首次就同一有毒物质(如镉和铬)对一种多毛类(如小头虫Capitellacapitata)两个在地理上隔离很远的种群(如太平洋东岸加利福尼亚长滩种群和太平洋西岸青岛种群)的效应进行的实验性研究.青岛种群和加州长滩种群铬的96小时半致死浓度分别为0.063mg/l和1.7mg/l.镉的96小时半致死浓度分别为1.0mg/l和0.6mg/l.对上述镉和铬两个种群的数值.讨论了敏感的原因。文章还对截至目前已发表的小头虫以及其它多毛类96小时半致死浓度的结果进行了比较.