Henry's law constants of phenol and mononitrophenols in water and aqueous sulfuric acid

Phenols are widely present in the atmosphere and nitration probably in the aerosol phase leads to nitrophenols. Nitration by nitric acid in sulfuric acid can be rapid, but little is known of the process under atmospheric conditions. The Henry's law constants K(H)(dagger) of phenol and 2-, 3- and 4-nitrophenol were all measured by a bubble stripping method as: 2820mol kg(-1) atm(-1) (at 298K), 147mol kg(-1) atm(-1) (at 298K), 1.6x10(4)mol kg(-1)atm(-1) (at 308K) and 2.1x10(4)mol kg(-1) atm(-1) (at 308K), respectively. The Henry's law constant of phenol in sulfuric acid systems is lower by more than a factor of two at 1020mol kg(-1) atm(-1) (at 298K) in 40wt% sulfuric acid, which is in line with salting-out of oxygen-containing aromatic compounds in water-sulfuric acid systems. The Henry's law constants of 2- and 4-nitrophenol behave differently and are almost independent of sulfuric acid concentration. The variation of K(H)(dagger) with temperature (T) described in terms of -dln(K(H)(dagger))/d(1/T) does not to vary with sulfuric acid concentration, suggesting enthalpy of dissolution for phenol is independent of sulfuric acid. The series of Henry's law constants measured here can describe the equilibrium situation for phenols in careful determinations of phase partitioning in the atmosphere.     

Effects of 2,4-dichlorophenol, pentachlorophenol and vegetation on microbial characteristics in a heavy metal polluted soil

The aim of this study was to evaluate the soil microbial characteristics in historically heavy-metal polluted soil, which was also affected by organic co-contaminants, 2,4-dichlorophenol or pentachlorophenol, which often occur due to the conventional use of pesticides. It was observed that the normalized microbial biomass (microbial biomass per unit soil organic C) of the contaminated soil was very low, less than 1% in both non-planted and ryegrass planted soil, and showed a decreasing trend with the treatment of organic co-contaminants. The microbial biomass and substrate-induced respiration (SIR) in the ryegrass planted soil were much larger, as compared with the non-planted soil with or without organic pollutants. The different resistant bacterial community and its physiological diversity in the rhizosphere further suggested that the effect of vegetation on microbial activity was not just a general increase in the mass or activity of pre-existing microorganisms, but rather acted selectively on microbial growth so that the relative abundance of different microbial groups in soil was changed. In sum, high concentrations of organic co-contaminants, especially pentachlorophenol (PCP), could strengthen the deterioration of microbial ecology. The adverse effect of heavy metal-organic pollutants on the soil microbial biomass and activity might be the reason for the slow degradation of PCP that has high chlorinated and high toxicity. Vegetation might be the efficient way to assist in improving and restoring the utilization of agricultural ecosystems. The beneficial microbial effect of vegetation could cause the rapid dissipation of 2,4-dichlorophenol (2,4-DCP) that has less chlorinated and less toxicity in the planted soils.     

Application of an enzyme-linked immunosorbent assay for the detection of clenbuterol residues in swine urine and feeds

The present study outlines applications of an enzyme-linked immunosorbent assay (ELISA) for the analysis of clenbuterol residues. Antisera were raised from rabbits immunized with diazotized clenbuterol-bovine serum albumin (BSA) conjugate. The assay was specific to clenbuterol with a half-maximum inhibition concentration (IC(50)) of 1.8 ng/mL and 2.5 ng/mL in blank swine urine and phosphate buffer solution, respectively. The assay had high cross-reactivity (86%) with mabuterol, but low with other adrenergic agonists and antagonists. The average recovery of clenbuterol, as measured with the ELISA, ranged from 90% to 112% in swine urine samples and from 86% to 95% in feeds, respectively. This new assay was compared with commercial ELISA test kits. An excellent correlation (r(2) = 0.98) between the two methods and satisfactory recoveries suggest that the new assay can be suitable for the determination of clenbuterol residues in real samples. The assay was used to analyze clenbuterol residues in 103 swine urine samples and 68 feed samples collected from northern China. Approximately 50% of the urine samples and 25% of the feed samples analyzed were found positive (concentration of clenbuterol > or = 1 ppb). The results indicate that clenbuterol was misused in some of the areas surveyed.     

Polychlorinated naphthalenes and coplanar polychlorinated biphenyls in tissues of harbor seals (Phoca vitulina) from the northern Gulf of Alaska

Blubber, liver and kidney samples of harbor seals (Phoca vitulina) from the northern Gulf of Alaska were collected during 2000-2001 for the analysis of polychlorinated naphthalenes (PCNs) and coplanar polychlorinated biphenyls (CoplPCBs). On the lipid weight (lw) base, the total concentrations of PCNs (Sigma PCNs) ranged from 0.3 to 27 ng/g lw, and the total concentrations of CoplPCBs (Sigma CoplPCBs) were 3.6-546 ng/g lw in all the tissue samples. Di-ortho PCBs and mono-ortho PCBs were dominant followed by non-ortho PCBs and PCNs. Sigma Mono-ortho PCBs and Sigma di-ortho PCBs in nursing seals were apparently lower than those in male adult seals, but Sigma PCNs and Sigma non-ortho PCBs in female adults were not significantly different from those in male adults. Differences in PCNs and CoplPCBs congener profiles in female and male adult seals are apparently related to their chemical structure and properties, animal's developmental stages and physiological conditions. A large quantity of mono-ortho and di-ortho PCBs might be transferred to newborns from the nursing seals during lactation, while non-ortho PCBs and PCNs were relatively accumulative in the mother seals. Sigma PCNs and Sigma CoplPCBs in the harbor seals correlated with ages, gender, body weight and blubber thickness, but the blubber Sigma PCNs and Sigma CoplPCBs in Kodiak Island and Southern Alaska Peninsula (KIAP) did not significantly differ from those in Prince William Sound (PWS). In addition to the new PCB data, this first report on PCN contamination in Alaskan harbor seal tissues is useful for the wildlife and ecosystem management and human health protection.     

Study of urban atmospheric pollution in Navarre (Northern Spain)

An ambient air quality study was undertaken in two cities (Pamplona and Alsasua) of the Province of Navarre in northern Spain from July 2001 to June 2004. The data were obtained from two urban monitoring sites. At both monitoring sites, ambient levels of ozone, NO_x, and SO₂ were measured. Simultaneously with levels of PM₁₀ measured at Alsasua (using a laser particle counter), PM₁₀ levels were also determined at Pamplona (using a beta attenuation monitor). Mean annual PM₁₀ concentrations in Pamplona and Alsasua reached 30 and 28 μg m⁻³, respectively. These concentrations are typical for urban background sites in Northern Spain. By using meteorological information and back trajectories, it was found that the number of exceedances of the daily PM₁₀ limit as well as the PM₁₀ temporal variation was highly influenced by air masses from North Africa. Although North African transport was observed on only 9% of the days, it contributed the highest observed PM₁₀ levels. Transport from the Atlantic Ocean was observed on 68% of the days; transport from Europe on 13%; low transport and local influences on 7%; and transport from the Mediterranean region on 3% of the days. The mean O₃ concentrations were 45 and 55 μg m⁻³ in Pamplona and Alsasua, respectively, which were above the values reported for the main Spanish cities. The mean NO and NO₂ levels were very similar in both sites (12 and 26 μg m⁻³, respectively). Mean SO₂ levels were 8 μg m⁻³ in Pamplona and 5 μg m⁻³ in Alsasua. Hourly levels of PM₁₀, NO and NO₂ showed similar variations with the typically two coincident maximums during traffic rush hours demonstrating a major anthropogenic origin of PM₁₀, in spite of the sporadic dust outbreaks.     

Cryptic species of Clavelina (Ascidiacea) in two different habitats: harbours and rocky littoral zones in the northwestern Mediterranean

Marinas and harbours provide ideal sites for the study of population genetics of marine invertebrates with restricted dispersal capabilities. They combine a confinement effect, particular ecological conditions (pollution, turbidity), and the possibility of high gene flow through ship-borne propagules, which greatly increases the natural dispersal capability of sexual and asexual propagules in many species with short-lived larvae. We studied the genetic structure of populations of the ascidian Clavelina lepadiformis living inside and outside harbours in the north-western Mediterranean. A 500-bp segment of the cytochrome c oxidase subunit I (COI) mitochondrial gene was sequenced in three populations from inside harbours (interior form) and in three populations from the rocky littoral (exterior form). Two congeneric Mediterranean species, Clavelina sp. and C. dellavallei, were used for comparison. We found that the interior and exterior forms of C. lepadiformis belong to two distinct clades, with a genetic divergence of 5%. Gene-flow values among these forms were insignificant. The lack of gene flow and the genetic divergence suggest that the interior and exterior forms of C. lepadiformis are in fact cryptic species rather than differentiated populations of the same species. Levels of gene flow were higher among interior habitats than among exterior habitats, a pattern likely maintained by genetic exchange through ships. We discuss the possible origins of the present-day distribution of these cryptic species. We contend that the study of species living both inside and outside these particular habitats will reveal more instances of genetic discontinuities allowing local adaptations.     

Simultaneous detection of enteric bacteria from surface waters by QPCR in comparison with conventional bacterial indicators

A rapid quantitative polymerase chain reaction (QPCR) method was developed for simultaneous detection of enteric bacteria from surface waters by utilizing a pair of universal primers which targeted four bacteria strains, namely Shigella dysenteriae, Vibrio cholerae, Salmonella typhimurium, and Escherichia coli. It was estimated that the QPCR method had a 94% confidence, and a detection limit as 2.7 E. coli cells per sample in undiluted DNA extracts. The QPCR method was applied for the bacteriological examination of several surface waters in the urban area of Xi'an, China and comparison was made with the conventional bacteria indicators determined by conventional membrane filter (MF) method. As a result, the calibrator cell equivalents (CCE) determined by QPCR was 2.2 to five times of the total coliform CFU, and the characteristics of the bacterial quality of different waters could be well presented by the QPCR results with a higher sensitivity. The coefficient of variation (CV) of data obtained by QPCR was smaller than that by traditional MF method, indicating a more stable analysis result. The QPCR method could thus be used as a supplement of the conventional culture method for more sensitive detection of pathogenic enteric bacteria from water.     

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005–2006

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (microg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 microg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 microg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 microg/l.     

Variability of total and available copper concentrations in relation to land use and soil properties in Yangtze River Delta of China

The effects of land use and soil properties on total and available Cu concentrations in soils were investigated in this study. A total of 276 surface (0-20 cm) soil samples were collected from seven land uses: industrial area, woodland, vegetable field, dry land, paddy field, tea garden and orchard. The total and available (DTPA extractable) Cu concentrations, pH, organic matter, and total nitrogen contents, and cation exchange capacity were measured for each sample. The correlation and ANOVA analyses showed that land use significantly affected total and available Cu concentrations, and the available ratio of soil Cu (available Cu concentration/total Cu concentration). On total Cu concentration, total nitrogen had significant influence in dry land and paddy field, and CEC in garden land; on available Cu concentration, the four measured soil properties showed significant influence only in paddy field; on the available ratio of Cu, pH had significant effect in paddy field and woodland, and CEC in industrial area. Moreover, the relationship between available Cu concentration and soil properties was constructed in different land uses. Spatial analysis of grain Cu using indicator Kriging showed that most of the study areas were in low risk for arable activities, and 7.94% of the study area and 5.10% of the arable land were in high risk probability.     

Phosphorus geochemistry in a Brazilian semiarid mangrove soil affected by shrimp farm effluents

Wastewater discharge from shrimp farming is one of the main causes of eutrophication in mangrove ecosystems. We investigated the phosphorus (P) geochemistry in mangrove soils affected by shrimp farming effluents by carrying out a seasonal study of two mangrove forests (a control site (CS); a site affected by shrimp farm effluents (SF)). We determined the soil pH, redox potential (Eh), total organic carbon (TOC), total phosphorus (TP), and dissolved P. We also carried out sequential extraction of the P-solid phases. In SF, the effluents affected the soil physicochemical conditions, resulting in lower Eh and higher pH, as well as lower TOC and higher TP than in CS. Organic P forms were dominant in both sites and seasons, although to a lesser extent in SF. The lower TOC in SF was related to the increased microbial activity and organic matter decomposition caused by fertilization. The higher amounts of P oxides in SF suggest that the effluents alter the dominance of iron and sulfate reduction in mangrove soils, generating more reactive Fe that is available for bonding to phosphates. Strong TP losses were recorded in both sites during the dry season, in association with increased amounts of exchangeable and dissolved P. The higher bioavailability of P during the dry season may be attributed to increased mineralization of organic matter and dissolution of Ca-P in response to more oxidizing and acidic conditions. The P loss has significant environmental implications regarding eutrophication and marine productivity.