The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

Mutagenicity evaluation of chemical pesticides

Abstract

Over the last few decades, the use of chemical pesticides has increased dramatically in the U.S. This relatively sudden increase greatly concerns the U.S. Environmental Protection Agency (EPA), since it has the responsibility for ensuring the safety of all pesticides used in the U.S. In response to this concern, EPA has established a review program, the Rebuttable Presumption Against Registration (RPAR), for periodically reassessing the mutagenic and carcinogenic potential of pesticide compounds.

This paper presents a review and evaluation of the data reported in the literature on six chemical pesticides suspect for mutagenic potential. The pesticide chemicals discussed are maleic hydrazide; rotenone; monuron; diallate; triallate, and benomyl.     

Accumulation of mercury and its effect on antioxidant enzymes in brain,liver, and kidneys of mice

Abstract

The effect of mercuric chloride (HgCl₂) on the activities of catalase, Superoxide dismutase (SOD), glutathione peroxidase (GPx), glutathione reductase (GR) and its effect on glutathione (GSH) content were evaluated in different organs (liver, kidneys, and brain) of mice after administration at 0, 0.25, 0.5 and 1.0 mg/kg/day for 14 days. The uptake of mercury shows that the kidneys accumulated the highest levels of mercury compare to brain and liver. The enzyme levels varied in mercury treated organs compare to control. A dose dependent increase of antioxidant enzymes occurred in the liver and kidneys. The increase in enzyme activities correlated with highest mercury accumulation in the kidneys and liver. Mercury is known to generate reactive oxygen species (ROS) in vivo and in vitro, therefore, it is likely that enzyme activities increased to scavenge ROS levels produced as a result of mercury accumulation. Glutathione content increased in liver and kidneys of mercury treated mice compare to control. The results showed that the highest oral dose of mercury significantly increased antioxidant enzymes in kidneys and liver. The increased antioxidant enzymes enhance the antioxidant potential of the organs to reduce oxidative stress.     

Phytotoxicity of atrazine and alachlor in soil amended with sludge,manure and activated carbon

Abstract

Greenhouse studies were conducted to determine the influence of waste‐activated carbon (WAC), digested municipal sewage sludge (DMS), and animal manure on herbicidal activity of atrazine [2‐chloro‐4‐(ethylamino)‐6‐(isopropylamino)‐s‐trazine] and alachlor [2‐chloro‐2’,6'‐diethyl‐N‐(methoxymethyl)acetanilide] in a Plainfield sandy soil. Amendments generally reduced bioactivity against oat (Avena sativa L.) and Japanese millet (E. crus‐galli frumentacea). The extent to which herbicide phytotoxicity was inhibited depended upon the application rate and the kind of soil amendment. WAC, applied at the loading rate of 2.1 mt C/ha, showed a significant inhibitory effect on both herbicides. In DMS‐ and manure‐amended soil, the reduction of atrazine activity was not significant at the rate of 8.4 mt C/ha, but reduction of alachlor activity was significant at the rate of 4.2 mt C/ha. Despite inhibition of herbicidal activity, the ED₅₀ of atrazine and alachlor was below 2 ppm in most of the amendment treatments. Before adopting carbon‐rich waste amendments as management practices for controlling pesticide leaching in coarse‐textured soils, further studies are needed to characterize how alterations in sorption, leaching and degradation may affect herbicidal activity.     

Feral swine disturbance at important archaeological sites

Feral swine are well known as environmentally destructive invasive animals in many areas around the world, where they degrade native habitats, harm rare plant and animal species, damage agricultural interests, and spread disease. We provide the first quantification of their potential as agents of disturbance at archaeological sites. Our study was conducted in south-central Florida at Avon Park Air Force Range, a base comprising over 40,000 ha and containing many archaeological sites. To determine the identifiable prevalence of feral swine disturbance, we examined 36 sites registered with the Florida State Historic Preservation Office and also eligible for inclusion in the National Register of Historic Places (NRHP). Moreover, we evaluated the extent of swine disturbance at a prehistoric site of extraordinary significance to Florida’s prehistory, “Dead Cow.” Fifteen of the 36 NRHP-eligible sites (42 %) had some level of swine disturbance, including 14 of 30 (47 %) sites known to have artifacts within 20 cm of the surface (well within swine rooting depths). At the Dead Cow site, we documented disturbance at 74 % of shovel test points. Sites with shallow artifact depositions appeared highly vulnerable to disturbance by feral swine, threatening destruction of artifact stratigraphy and provenience. Our observations likely are a minimal representation of accumulated damage. These irreplaceable sites tell the area’s land use story across the millennia. That they are under threat from feral swine should serve broad notice of potential threats that feral swine may pose to archaeological sites globally, making effective swine management imperative for site protection.     

Contamination of the River Ganga and its toxic implication in the blood parameters of the major carp Labeo rohita (Ham)

A field study was conducted to examine different physicochemical properties of water and various haematological and biochemical parametres of the fish Labeo rohita collected from the Ganga River (National river of India) at Varanasi district, India. The water was found to be greatly contaminated with a number of dissolved metals (Fe, Cr, Zn, Cu, Mn, Ni and Pb) whose concentrations were above the safe limits suggested by Bureau of Indian Standard (BIS 1991) for drinking water (Fe, 1,353.33 %; Cr, 456 %; Mn, 553.33 %; Ni, 4,490 % and Pb, 1,410 %). The metal accumulation in the fish blood was very high (Fe, 2,408 %; Cr, 956.57 %; Zn, 464.90 %; Cu, 310.57 %; Mn, 1,115.48 %) in comparison to the control fish maintained under strict quality control. Lower values of the various haematological parameters (total erythrocytes count, haemoglobin, haematocrit, mean corpuscular volume and O₂-carrying capacity) in the river fish in comparison to the control indicate toxic manifestation exerted by the contaminated river water on the fish. The higher level of total leucocytes count further illustrates stressed condition of the river fish. The toxic impact of the Ganga water is also expressed in the fish by the presence of higher levels of cholesterol, glucose, elevated activities of the enzymes aspartate amino transferase and alanine amino transferase, and lowered protein concentration.     

Bioaccumulation of perfluoroalkyl acids in dairy cows in a naturally contaminated environment

Beef and dairy products may be important vectors of human exposure to perfluoroalkyl acids (PFAAs), but the understanding of how PFAAs are accumulated and transferred through agricultural food chains is very limited. Here, the bioaccumulation of PFAAs in dairy cows receiving naturally contaminated feed and drinking water was investigated by conducting a mass balance of PFAAs for a herd of dairy cows in a barn on a typical Swedish dairy farm. It was assumed that the cows were able to reach steady state with their dietary intake of PFAAs. Perfluorooctane sulfonic acid (PFOS) and perfluoroalkyl carboxylic acids (PFCAs) with 8 to 12 carbons were detected in cow tissue samples (liver, muscle, and blood) at concentrations up to 130 ng kg^?1. Mass balance calculations demonstrated an agreement between total intake and excretion within a factor of 1.5 and consumption of silage was identified as the dominant intake pathway for all PFAAs. Biomagnification factors (BMFs) were highly tissue and homologue specific. While BMFs of PFOS and PFCAs with 9 and 10 fluorinated carbons in liver ranged from 10 to 20, perfluorooctanoic acid (PFOA) was not biomagnified (BMF?<?1) in any of the investigated tissues. Biotransfer factors (BTFs; defined as the concentration in tissue divided by the total daily intake) were calculated for muscle and milk. Log BTFs ranged from ?1.95 to ?1.15 day kg^?1 with the highest BTF observed for PFOS in muscle. Overall, the results of this study suggest that long-chain PFAAs have a relatively high potential for transfer to milk and beef from the diet of dairy cows. However, a low input of PFAAs to terrestrial systems via atmospheric deposition and low bioavailability of PFAAs in soil limits the amount of PFAAs that enter terrestrial agricultural food chains in background contaminated environments and makes this pathway less important than aquatic exposure pathways. The BTFs estimated here provide a useful tool for predicting human exposure to PFAAs via milk and beef under different contamination scenarios.     

Misuse of null hypothesis significance testing: would estimation of positive and negative predictive values improve certainty of chemical risk assessment?

Although generally misunderstood, the p value is the probability of the test results or more extreme results given H₀ is true: it is not the probability of H₀ being true given the results. To obtain directly useful insight about H₀, the positive predictive value (PPV) and the negative predictive value (NPV) may be useful extensions of null hypothesis significance testing (NHST). They provide information about the probability of statistically significant and non-significant test outcomes being true based on an a priori defined biologically meaningful effect size. The present study explores the utility of PPV and NPV in an ecotoxicological context by using the frequently applied Daphnia magna reproduction test (OECD guideline 211) and the chemical stressor lindane as a model system. The results indicate that especially the NPV deviates meaningfully between a test design strictly following the guideline and an experimental procedure controlling for α and β at the level of 0.05. Consequently, PPV and NPV may be useful supplements to NHST that inform the researcher about the level of confidence warranted by both statistically significant and non-significant test results. This approach also reinforces the value of considering α, β, and a biologically meaningful effect size a priori.     

Water quality characteristics of discharge from reforested loose-dumped mine spoil in eastern Kentucky

Surface mining is a common method for extracting coal in the coal fields of eastern Kentucky. Using the Forestry Reclamation Approach (FRA), which emphasizes the use of minimally compacted or loose-dumped spoil as a growth medium for trees, reclamation practitioners are successfully reestablishing forests. Yet, questions remain regarding the effects FRA has on the quality of waters discharged to receiving streams. To examine the effect of FRA on water quality, this study compared waters that were discharged from three types of spoils: predominantly brown, weathered sandstone (BROWN); predominantly gray, unweathered sandstone (GRAY); and an equal mixture of both aforementioned sandstones and shale (MIXED). The water quality parameters pH, EC, Ca, K, Mg, Na, NO-N, NH-N, SO, Cl, TC, suspended sediment concentration (SSC), settleable solids (SS), and turbidity were monitored over a 2-yr period on six 0.4-ha plots (two replications per spoil type). Generally, levels of Cl, SO, Ca, NO-N, NH-N, SS, SSC, and turbidity decreased over time. The pH for all spoils increased from about 7.5 to 8.5. The EC remained relatively level in the BROWN spoil, whereas the GRAY and MIXED spoils had downward trajectories that were approaching 500 μS cm. The value of 500 μS cm has been reported as the apparent threshold at which certain taxa such as Ephemeroptera (e.g., Mayfly) recolonize disturbed headwater streams of eastern Kentucky and adjacent coal-producing Appalachian states.     

A simple model to assess nitrogen and phosphorus contamination in ungauged surface drainage networks: application to the Massaciuccoli Lake Catchment, Italy

Modeling is a common practice to evaluate factors affecting water quality in environmental systems impaired by point and nonpoint losses of N and P. Nevertheless, in situations with inadequate information, such as ungauged basins, a balance between model complexity and data availability is necessary. In this paper, we applied a simplified analytical model to an artificially drained floodplain in central-western Italy to evaluate the importance of different nutrient sources and in-stream retention processes and to identify critical source areas. We first considered only a set of chemical concentrations in water measured from February through May 2008 and from November 2008 through February 2009. We then broadened available data to include water discharge and hydraulic-head measurements to construct a hydrogeological model using MODFLOW-2000 and to evaluate the reliability of the simplified method. The simplified model provided acceptable estimates of discharge (ranging from 0.03-0.75 m s) and diffuse nutrient inputs from water table discharge and in-stream retention phenomena. Estimates of PO-P and total P retention (ranging from 1.0 to 0.6 μg m s and from 1.18 to 0.95 μg m s for PO-P and total P, respectively) were consistent with the range of variability in literature data. In contrast, the higher temporal variability of nitrate concentrations decreased model accuracy, suggesting the need for more intensive monitoring. The model also separated the dynamics of different reaches of the drainage network and identified zones considered critical source areas and buffer zones where pollutant transport is reduced.