Making performance-based chemistry work: how we created comparable data among laboratories as part of a Southern California marine regional assessment

Quality assurance procedures to ensure consistency among chemistry laboratories typically involves the use of standard methods and state certification programs that require laboratories to demonstrate their ability to attain generic performance criteria. To assess whether these procedures are effective for ensuring comparability when processing local samples with potentially complex matrices, seven experienced, state-certified laboratories participated in an intercalibration exercise. Each laboratory was permitted to use their typical methodology for quantifying PAH, PCB and DDT on shared samples collected from Santa Monica Bay and the Palos Verdes Shelf, two sites with a complex mix of constituents. In the initial intercalibration exercise, results from these laboratories differed by as much as an order of magnitude for all three chemical groups. Much, but not all, of the difference was attributable to differences in detection capability. A series of studies was conducted to identify the reasons for the observed differences, which varied among laboratories and included methodological differences, instrument sensitivity differences, and differing interpretations of chromatograms. Following these investigations and resulting modifications to laboratory procedures, the exercise was repeated. The average coefficient of variation among laboratories across all chemical parameters was reduced to less than 30%. Our results suggest that performance-based chemistry can produce comparable results, but the certification processes presently in place that focus on general laboratory procedures and simple matrices are insufficient to achieve comparability.     

An indicative method for determination of the most hazardous changes in slopes of the subsidence basins in underground coal mining area in Ostrava (Czech Republic)

Considering growing population and decreasing mineral resource reserves, the issue of undermining has been and shall remain very topical. This study aims to identify the mutual connections between mined out panels of a deposit and the final manifestations on the ground surface related to deep black coal mining. On the grounds of the identified connections, the study describes a method to simplify a common evaluation of undermined areas according to building site categories. Within the study, a demarcation of the areas was conducted in two localities in Czech Republic influenced by the effects of undermining in the Upper-Silesian Basin. In the allotment of the CSM Mine, an area unsuitable for founding structures was defined from the centre of the worked out workings to the distance of 175 m from the panel's edge, for which the corresponding break angle is 78.3°. Similarly, in the allotment of the Paskov Mine, an area unsuitable for founding structures was determined to the distance of 500 m from the panel's edge, for which the corresponding break angle is 50.2°. This demarcation may be implemented prior to deposit mining being aware of several physical-mechanical parameters of rocks in the deposit's overburden. Having mined out a particular section of a deposit, it is recommended to verify the values of break angle using the method described herein. The study may be applied as a relatively fast and effective method to evaluate future land use for planning.     

Improving National-Scale Carbon Stock Inventories Using Knowledge on Land Use History

National-scale inventories of soil organic carbon (SOC) and forest floor carbon (FFC) stocks have a high uncertainty. Inventories are often based on the interpolation of sampled information, often using a number of covariables to help such interpolation. The rationale for the choice of these covariables is not always documented, despite the fact that many local-scale studies have identified the factors explaining spatial variability of SOC and FFC stocks. These studies indicate, among others the importance of long-term land use history. Despite this, information on the effects of land use history has never been used to explain variability of carbon stocks in national-scale inventories. We designed an alternative method to improve national-scale inventories of SOC and FCC for the Dutch sand area that takes stock of the findings of detailed case studies. Determinants for SOC and FFC stocks derived from landscape-scale case studies were used to map national-scale spatial variability and to calculate national totals. The resulting national-scale spatial distribution was compared with the SOC stock map from the current Dutch greenhouse gas inventory. Using land use history to explain SOC variability decreased the error of the SOC stock estimate in 60 % of the area. The error in FFC stocks decreased in half of the forest area after including soil fertility, tree species, and forest age as explanatory factors. Estimates with reduced uncertainty will make land use and land management a more attractive and acceptable mitigation option to reduce emissions of greenhouse gases for the LULUCF sector.     

Statewide Survey of Hormones and Antibiotics in Surface Waters of Delaware

Water‐quality surveys have confirmed the presence of hormones and antibiotics in surface waters of the United States, which may be of concern to aquatic life. We investigated the concentrations of hormones and antibiotics in surface waters of the state of Delaware to determine – how they compared against environmental thresholds, how they varied across the state, and if they were correlated with land use type. Fifty surface water locations were sampled during early spring and late summer. Water samples were initially screened with ELISA followed by analysis with LC/MS/MS. The measured ranges of hormone concentrations were: 0‐3.71 ng/l for estrone, 0‐4.65 ng/l for estrone‐3‐sulfate, and 0‐6.27 ng/l for 17β‐estradiol. The measured ranges of antibiotics were: 0‐3.30 ng/l for sulfamerazine, 0‐10.74 ng/l for sulfamethoxazole, and 0‐2.29 ng/l for tetracycline. The predicted no‐effect concentration (PNEC) for estrone was exceeded for three samples and the PNEC for 17β‐estradiol was exceeded for 11 samples. In general, concentrations and detection frequencies were lower in the summer than the spring. The highest concentrations of hormones and antibiotics were spatially distributed in agricultural and urban areas; however, the correlations between land use type and the concentrations were weak. This study was the first statewide survey of hormones and antibiotics for Delaware and provided important baseline data on these emerging contaminants.     

Role of nitric oxide in the genotoxic response to chronic microcystin-LR exposure in human–hamster hybrid cells

Microcystin-LR (MC-LR) is the most abundant and toxic microcystin congener and has been classified as a potential human carcinogen (Group 2B) by the International Agency for Research on Cancer. However, the mechanisms underlying the genotoxic effects of MC-LR during chronic exposure are still poorly understood. In the present study, human–hamster hybrid (A_L) cells were exposed to MC-LR for varying lengths of time to investigate the role of nitrogen radicals in MC-LR-induced genotoxicity. The mutagenic potential at the CD59 locus was more than 2-fold higher (p < 0.01) in A_L cells exposed to a cytotoxic concentration (1 μmol/L) of MC-LR for 30 days than in untreated control cells, which was consistent with the formation of micronucleus. MC-LR caused a dose-dependent increase in nitric oxide (NO) production in treated cells. Moreover, this was blocked by concurrent treatment with the NO synthase inhibitor N^G-methyl-l-arginine (l-NMMA), which suppressed MC-LR-induced mutations as well. The survival of mitochondrial DNA-depleted (ρ⁰) A_L cells was markedly decreased by MC-LR treatment compared to that in A_L cells, while the CD59 mutant fraction was unaltered. These results provided clear evidence that the genotoxicity associated with chronic MC-LR exposure in mammalian cells was mediated by NO and might be considered as a basis for the development of therapeutics that prevent carcinogenesis.     

A technique for estimating one-dimensional diffusion coefficients in low-permeability sedimentary rock using X-ray radiography: comparison with through-diffusion measurements

The measurement of diffusive properties of low-permeability rocks is of interest to the nuclear power industry, which is considering the option of deep geologic repositories for management of radioactive waste. We present a simple, non-destructive, constant source in-diffusion method for estimating one-dimensional pore diffusion coefficients (D(p)) in geologic materials based on X-ray radiography. Changes in X-ray absorption coefficient (Deltamicro) are used to quantify changes in relative concentration (C/C(0)) of an X-ray attenuating iodide tracer as the tracer solution diffuses through the rock pores. Estimated values of D(p) are then obtained by fitting an analytical solution to the measured concentration profiles over time. Measurements on samples before and after saturation with iodide can also be used to determine iodide-accessible porosity (phi(I)). To evaluate the radiography method, results were compared with traditional steady-state through-diffusion measurements on two rock types: shale and limestone. Values of D(p) of (4.8+/-2.5)x10(-11) m(2).s(-1) (mean+/-standard deviation) were measured for samples of Queenston Formation shale and (2.6+/-1.0)x10(-11) m(2).s(-1) for samples of Cobourg Formation limestone using the radiography method. The range of results for each rock type agree well with D(p) values of (4.6+/-2.0)x10(-11) m(2).s(-1) for shale and (3.5+/-1.8)x10(-11) m(2).s(-1) for limestone, calculated from through-diffusion experiments on adjacent rock samples. Low porosity (0.01 to 0.03) and heterogeneous distribution of porosity in the Cobourg Formation may be responsible for the slightly poorer agreement between radiography and through-diffusion results for limestones. Mean values of phi(I) for shales (0.060) and limestones (0.028) were close to mean porosity measurements made on bulk samples by the independent water loss technique (0.062 and 0.020 for shales and limestones, respectively). Radiography measurements offer the advantage of time-saving for diffusion experiments because the experiment does not require steady-state conditions and also allows for visualization of the small-scale heterogeneities in diffusive properties within rocks at the mm to cm scale.     

Phytoremediation of an aged petroleum contaminated soil using endophyte infected and non-infected grasses

Phytoremediation is a promising technique for cleaning petroleum contaminated soils. In this study, the effects of two grass species (Festuca arundinacea Schreb. and Festuca pratensis Huds.), infected (E(+)) and non-infected (E(-)) by endophytic fungi (Neotyphodium coenophialum and Neotyphodium uncinatum, respectively) on the degradation of petroleum hydrocarbons in an aged petroleum contaminated soil was investigated. Plants were grown in the soil for 7 months and unplanted soil considered as control. At the end of the experiment, total and oil-degrading bacteria, dehydrogenase activity, water-soluble phenols, total petroleum hydrocarbons (TPH) and polycyclic aromatic hydrocarbons (PAHs) contents were measured in the soil. The results demonstrated that E(+) plants contained more root and shoot biomass than E(-) plants and created higher levels of water-soluble phenols and dehydrogenase activity in the soil, while there was no significant difference in bacterial counts of planted soils. Planting stimulated total and oil-degrading bacterial numbers, dehydrogenase activity and the soil content of water-soluble phenols. Regardless of endophyte infection, PAH and TPH removal in the rhizosphere of plants were 80-84 and 64-72% respectively, whereas the removals in controls were 56 and 31%, respectively. It was revealed that TPHs in retention time range of n-alkanes with C(10)-C(25) chain lengths and TPH were more degraded in the rhizosphere of E(+) plants compared to E(-) ones. Thus, grasses infected with endophytic fungi could be more efficient for removal of TPH from oil-contaminated soils.