Sample size and power determination for detecting interactions in mixtures of chemicals

In the analysis of mixtures of drugs/chemicals it is often of interest to test for the presence of interaction. If the hypothesis of no interaction (additivity) is not rejected, then the analyst may reasonably claim additivity if and only if the study is powered to a desired (e.g., biologically meaningful) level. The objective of this article is to address the sample size and power issues related to testing the hypothesis of additivity at specified mixture points. The study of disinfectant by-products (DBPs) found in drinking water, described in earlier literature, is used to illustrate the procedures for estimating power and sample sizes for detecting interactions at specified mixtures. The four trihalomethanes used in the study are bromodichloromethane (BDCM), chlorodibromomethane (CDBM), chloroform (CHCl₃), and bromoform (CHBr₃)     

Temporal change in soil macropores measured using tension infiltrometer under different land uses and slope positions in subtropical China

Purpose

Soil macropores play a principal role in water infiltration but they are highly variable. The objectives of this study were (1) to investigate the temporal change in macropores of an Ultisol as affected by land use and slope position and (2) to analyze contribution of macropores to water infiltration.

Materials and methods

Water infiltration was measured at upper and lower slopes in citrus orchard and watermelon field once every 2 months for 1 year using tension infiltrometers at a successive pressure head from ?12, ?6, ?3, to 0 hPa.

Results and discussion

Hydraulic conductivity (K) was significantly affected by land use and slope position except at 0 hPa pressure head, showing a significant temporal variation. Effective macroporosity, derived from the increment of hydraulic conductivity between ?3 and 0 hPa, showed a significant temporal variation. Such temporal variation was land use (P?<?0.05) and slope position (P?<?0.001) dependent. Despite of low proportion in total soil volume (averaged 3.5 cm³ m^?3), the macropores contributed 47 % of water flux on average. The macroporosity was more stable and higher in the citrus orchard (2.43 cm³ m^?3, coefficient of variance (CV)?=?75 %) than in the watermelon field (1.72 cm³ m^?3, CV?=?117 %) and contributed more to infiltration in the citrus orchard (60 %, CV?=?16 %) than in the watermelon field (33 %, CV?=?43 %) as well, because tillage was operated only in the watermelon field.

Conclusions

No-tillage increased water conducting macropores but did not increase hydraulic conductivity irrespective of slope position.

     

Sustainability of in situ remediation of Cu- and Cd-contaminated soils with one-time application of amendments in Guixi,China

Purpose

In situ immobilization of heavy metal-contaminated soils with the repeated incorporation of amendments can effectively reduce the bioavailability of soil heavy metals. However, the long-term application of amendments would lead to the destruction of soil structure and accumulation of soil toxic elements, ultimately affecting food security and quality. Thus, the sustainability of the amendments in a heavy metal-contaminated soil was evaluated from 2010 to 2012.

Materials and methods

Batch field experiments were conducted in the soils, which were amended with apatite (22.3 t ha^?1), lime (4.45 t ha^?1), and charcoal (66.8 t ha^?1), respectively. The amendments were applied only one time in 2009, and ryegrass was sown each year. Ryegrass and setaria glauca (a kind of weed) were harvested each year. Concentrations of copper (Cu) and cadmium (Cd) were determined by batch experiments. Five fractions of Cu and Cd were evaluated by a sequential extraction procedure.

Results and discussion

Ryegrass grew well in the amended soils in the first year, but it failed to grow in all the soils in the third year. However, setaria glauca could grow with higher biomass in all the amended soils. The treatment of apatite combined with plants was more effective than lime and charcoal treatments in removing Cu and Cd from the contaminated soils by taking biomass into account. Apatite had the best sustainable effect on alleviating soil acidification. The Cu and Cd concentrations of CaCl₂-extractable and exchangeable fractions decreased with the application of amendments. Moreover, apatite and lime could effectively maintain the bioavailability of Cu and Cd low.

Conclusions

Apatite had a better sustainable effect on the remediation of heavy metal-contaminated soils than lime and charcoal. Although all the amendment treated soils did not reduce soil total concentrations of Cu and Cd, they could effectively reduce the environmental risk of the contaminated soils. The findings could be effectively used for in situ remediation of heavy metal-contaminated soils.

     

Characterisation of agricultural drainage ditch sediments along the phosphorus transfer continuum in two contrasting headwater catchments

Purpose

This study investigated the phosphorus (P) source, mobilisation and transport potential of ditch bed sediments as well as surrounding field and bank soils in two agricultural headwater catchments with contrasting soil drainage capacities. This information is important for discerning the potential for ditches to attenuate or augment transfers of P from upstream sources and thus for developing appropriate management strategies for these features.

Materials and methods

Phosphorus sources were characterised using the Mehlich3-P, water-soluble P and total P tests. Phosphorus mobilisation potential was characterised using the Mehlich3-AL/P, Mehlich3-Ca/P and DESPRAL P tests. Phosphorus transport potential was characterised using data collected on the presence/absence of surface water in ditches during field surveys and downstream turbidity data.

Results and discussion

Ditch sediments had similar P source contents (Mehlich3-P, water-soluble P and total P) to the surrounding field soils and higher P contents than bank soils. However, calcium contents of sediments in the poorly drained catchment reflected the deep sub-soils rather than the surrounding field and bank soils. Mehlich3-Al/P and Mehlich3-Ca/P contents of ditch sediments in the well (non-calcareous) and poorly (calcareous) drained catchments respectively indicated potential for P retention (above thresholds of 11.7 and 74, respectively). However, sediments were less aggregated than field soils and may mobilise more particulate P (PP) during rain events. Nevertheless, the majority of surveyed ditches dried out from March to September 2011; thus, their potential to mobilise PP may be less important than their capacity to attenuate soluble and PP during this time.

Conclusions

In these and similar catchments, soluble P attenuation and particulate P mobilisation should be maximised and minimised, respectively, for example, by cleaning out the sediments before they become saturated with P and encouraging vegetation growth on ditch beds. This study also highlighted the influence of deep sub-soils on soluble P retention in ditches and thus the utility of characterising soils below depths normally included in soil classifications.

     

Characterization of suspended particulate matter in the Moselle River (Lorraine,France): evolution along the course of the river and in different hydrologic regimes

Purpose

Suspended particulate matter (SPM) plays an important role in the transport and fate of contaminants in the environment. To better understand the relationships between contaminants and SPM, SPM properties, and their variations with flow regime, river size, land use, and season should be considered.

Materials and methods

The grain size distribution, elemental composition, and mineralogy of SPM from different stations along the Moselle River (Lorraine, France) were investigated at the particle scale during different flow regimes. The resulting data were compared with the elemental composition of the dissolved compartment to understand the role of particles in element transport.

Results and discussion

The grain size distribution, elemental composition, and mineralogy of SPM along the Moselle River and during different flow regimes showed only slight variations, except for the Fensch and Orne tributaries, two rivers that were impacted by inherited steel-making industrialization and different land use. In the Moselle River, SPM mainly consisted of clay minerals, while in Fensch and Orne Rivers, SPM mainly consisted of multiple types of anthropogenic particles. The diffuse urbanization gradient was hardly recognized based on the Trace Metal Element (TMEs) content in the river SPM, while the rivers impacted by the steel industries had greater TME contents. Finally, the TME content in the Moselle SPM was more strongly influenced by water flow than by the position of sampling on the linear reach of the Moselle River. The partitioning of TMEs in the particles and water at the main Moselle station (Frouard) revealed that SPM predominantly contributed to TMEs transport.

Conclusions

This study confirmed that catchment geology greatly contributed to the SPM composition in the mean-sized rivers. In addition, the high anthropogenic pressure could be deciphered for small tributaries. Furthermore, this study allowed us to observe the high contribution of particles to TMEs and Rare Earth Element (REEs) transportation.

     

Interaction of contaminated sediment from a salt marsh with estuarine water: evaluation by leaching and ecotoxicity assays and salts from leachate evaporation

Purpose

Wastes from a former Portuguese steel plant were deposited between 1961 and 2001 on the riverbank of a tributary of the Tagus River creating a landfill connected to the river, posing a potential contamination risk to the Tagus estuary ecosystem. This study aims to assess the transfer of chemical elements from contaminated sediments to the estuarine water from cycles of sediment leaching so as to evaluate the ecotoxicity of the leachates, and to analyze the solid phases crystallized from those leachates.

Materials and methods

Landfill sediment and estuarine water samples were collected during low tide. Sediment samples were analyzed for pH, electric conductivity (EC), C_org, NPK, and iron oxides. Leaching assays (four replicates) were done using estuarine water (200 cm³/replicate) and 1.5 kg of sediment per reactor. Each reactor was submitted to four leaching processes (0, 28, 49, and 77 days). The sediment was kept moist between leaching processes. Sediment (total (acid digestion) and available fraction (diluted organic acid extraction-Rhizo)) elemental concentrations were determined by inductively coupled plasma–instrumental neutron activation analysis (ICP/INAA). Leachates, and estuarine and sediment pore waters were analyzed for metals/metalloids by ICP/mass spectrometry (MS) and carbonates/sulfate/chloride by standard methodologies. Ecotoxicity assays were performed in leachates and estuarine and pore waters using Artemia franciscana and Brachionus plicatillis. Aliquots of the leachates were evaporated to complete dryness (23–25 °C) and crystals analyzed by X-ray powder diffraction (XRD).

Results and discussion

Sediment with pH?=?8 and high EC and C_org was contaminated with As, Cd, Cr, Cu, Pb, and Zn. The element concentrations in the available fraction of the sediment were low compared to the sediment total concentrations (<1 % for Rhizo extraction). The concentrations of potentially hazardous elements in the estuarine water were relatively low, except for Cd. Concentrations of hazardous elements in the leachates were very low. Calcium, K, Mg, Na, and chloride concentrations were high but did not vary significantly among the four leaching experiments. Total concentrations of carbonate were much higher in leachates than in estuarine water. Both estuarine water and leachates showed negligible toxicity. Crystals identified in the solids obtained from the leachates by evaporation were halite, anhydrite, epsomite, dolomite, and polyhalite.

Conclusions

The sediment showed the capacity to retain the majority of the potentially hazardous chemical elements. Remobilization of chemical elements from sediment by leaching was essentially negligible. The variation of total concentrations of Ca, carbonate, and sulfate in leachates indicates that the sediment contained reactive sulfides. Due to its composition, the sediment seems to be a dynamic system of pollution control, which should not be disturbed.

     

Investigation of sorbate-induced plasticization of Pahokee peat by solid-state NMR spectroscopy

Purpose

Sorbate-induced swelling and plasticization of sorbent have been linked to sorption hysteresis of organic compounds in the natural organic matter of isolated humic acids, soils, and coals. The above processes, which have important implications for the fate and bioavailability of organic and inorganic contaminants, are mostly based on macroscopic changes and require molecular-level confirmation. This study aimed to investigate the presence or absence of sorbate-induced plasticization of Pahokee peat soil as a function of different sorbates.

Materials and methods

The plasticization of Pahokee peat soil was studied upon sorption of different proton-free solutes including C₆D₆, CDCl₃, CCl₄, C₂Cl₄, CBr₄, C₆D₅Cl, and C₅D₅N, covering apolar and polar aromatic and aliphatic compounds. The swelling and plasticization of Pahokee peat soil were verified at the molecular level by ¹H wideline and two-dimensional wideline separation (2D WISE) NMR. The use of ¹H wideline shapes is the traditional technique for studying molecular dynamics but hampered by the lack of spectral resolution, with one dimension displaying ¹³C chemical shifts and the second showing ¹H wideline shapes, is capable of providing information on molecular dynamics of specific functional groups.

Results and discussion

Our results showed that the segments of Pahokee peat soil sorbed with C₆D₆, C₂Cl₄, and C₅D₅N became more mobile, but the changes due to the plasticization were small. Both C₆D₆ and C₅D₅N selectively increased the mobility of specific components, C₆D₆ of the nonpolar alkyl domains, and C₅D₅N of both the nonpolar alkyl domains and aromatic components.

Conclusions

Some liquid solutes at high concentrations (2–5 wt%) are capable of slightly “softening” natural organic matter of a soil, and this provides support for the hypothesis that natural organic matter in Pahokee peat soil is in a glassy state that is subject to plasticization.

     

Bayesian Semiparametric Model for Pathway-Based Analysis with Zero-Inflated Clinical Outcomes

In this paper, we propose a semiparametric regression approach for identifying pathways related to zero-inflated clinical outcomes, where a pathway is a gene set derived from prior biological knowledge. Our approach is developed by using a Bayesian hierarchical framework. We model the pathway effect nonparametrically into a zero-inflated Poisson hierarchical regression model with an unknown link function. Nonparametric pathway effect was estimated via a kernel machine, and the unknown link function was estimated by transforming a mixture of the beta cumulative density function. Our approach provides flexible nonparametric settings to describe the complicated association between gene expressions and zero-inflated clinical outcomes. The Metropolis-within-Gibbs sampling algorithm and Bayes factor were adopted to make statistical inferences. Our simulation results support that our semiparametric approach is more accurate and flexible than zero-inflated Poisson regression with the canonical link function, which is especially true when the number of genes is large. The usefulness of our approach is demonstrated through its applications to the Canine data set from Enerson et al. (Toxicol Pathol 34:27–32, 2006). Our approach can also be applied to other settings where a large number of highly correlated predictors are present.Supplementary materials accompanying this paper appear on-line.     

Blind inlets: conservation practices to reduce herbicide losses from closed depressional areas

Purpose

In a 6-year study, we investigated the effectiveness of blind inlets as a conservation practice in reducing pesticide losses compared to tile risers from two closed farmed depressional areas (potholes) in the US Midwest under a 4-year cropping rotation.

Materials and methods

In two adjacent potholes within the same farm and having similar soils, a conventional tile riser and blind inlet were installed. Each draining practice could be operated independent of each other in order to drain and monitor each depression with either practice. Sampling events (runoff events) were collected from the potholes from 2008 to 2013 using autosamplers. The samples were analyzed for atrazine, metolachlor, 2,4-D, glyphosate, and deethylatrazine.

Results and discussion

The results of this study demonstrated that the blind inlet reduced analyzed pesticide losses; however, the level of reduction was compound dependent: atrazine (57 %), 2,4-D (58 %), metolachlor (53 %), and glyphosate (11 %).

Conclusions

Results from this study corroborate previous research findings that blind inlets are an effective conservation practice to reduce discharge and pollutants, including pesticides from farmed pothole surface runoff in the US Midwest.

     

Genetic diversity in <Emphasis Type="Italic">Eremostachys superba</Emphasis> Royle ex Benth. (Lamiaceae), an endangered Himalayan species,as assessed by RAPD

Eremostachys superba Royle ex Benth. (Lamiaceae) has undergone a severe decline in population size since its discovery in the North-western Himalayas in late 19th century. One hundred and seventy-two plants from six populations in the Indian states of Uttar Pradesh and Jammu & Kashmir, located between 0.45 km and 455.72 km apart from each other were evaluated for RAPD polymorphism. Sixteen random primers generated 92 bands overall, 77 of which were polymorphic. Shannon’s index of genetic diversity within populations (H _o) ranged between 0.305 and 0.421; the average within-population diversity (H _pop) was 0.389; and the total species diversity (H _sp) was 0.478. The population from Mohand (representing the type locality) had the fewest plants, at 18, and was genetically the most depauperate. Among the other populations, ranging in size between 52 and 1,022 individuals, no relation between population size and genetic diversity was evident. It is suggested that these six populations represent relics of a larger, extended population, in which the presence of perennating rootstocks has helped preserve historic patterns of genetic diversity. AMOVA revealed that 83.01% of the variation exists within populations, which was consistent with earlier studies on the reproductive biology of E. superba, which indicated this species is predominantly allogamous. FST distances between all populations were significant, indicating geographic differentiation despite some of them being closely separated. Habitat restoration and protection from indiscriminate harvesting are proposed as primary strategies for conserving E. superba. Rejuvenation of the Mohand population through intrapopulation crossing between plants bearing diverse molecular phenotypes is also suggested.