Hexachlorocyclohexanes (HCHs) in the Canadian Archipelago. 2. Air-water gas exchange of alpha- and gamma-HCH

Air and water were sampled in the Canadian Archipelago during summer on the Tundra Northwest 1999 (TNW-99) expedition and air was sampled at Resolute Bay (RB), Nunavut, to determine the gas exchange of alpha- and gamma-hexachlorocyclohexanes (HCHs) and the enantiomers of alpha-HCH. Air concentrations of sigmaHCH during TNW-99 and at RB were similar, averaging 55 and 53 pg m(-3), respectively. The net gas exchange direction was volatilization for alpha-HCH and near equilibrium or deposition for gamma-HCH, whereas actual fluxes depended on the fraction of open water. Enantiomer fractions, EF = (+)/[(+) + (-)] of alpha-HCH in air sampled from shipboard were significantly correlated to those in surface water for events with >90% open water, but were closer to racemic and not correlated to EFs in water for events with 0-50% open water. Levels of alpha-HCH in air at RB averaged 37 +/- 9 pg m(-3) from June to early July, and EFs were close to racemic (0.496 +/- 0.004). In mid-July the ice pack broke up around RB. From this point through August, air concentrations increased significantly to 53 +/- 5 pg m(-3), and the mean EF decreased significantly to 0.483 +/- 0.009. Air concentrations of gamma-HCH at RB did not differ significantly before (8.0 +/- 3.7 pg m(-3)) and after (6.6 +/- 0.76 pg m(-3)) ice breakup. Results show that alpha-HCH enantiomers are sensitive tracers for following the impact of ice cover loss on gas exchange in the Arctic.     

Kaffircorn malting and brewing studies. XVI. The distribution and activity of alpha- and beta- amylases in germinating kaffircorn

Unlike barley which possesses β-amylase activity before germination, sorghum grain is devoid of this enzyme. Both α- and β-amylase are produced during the germination of sorghum and, in any particular malting trial, the ratio of the enzymes to one another remains approximately constant throughout the trial. The actual value at which the ratio remains constant depends on the temperature of the malting and the variety but not on the watering treatment given during malting. The amylase concentration in the embryo is usually higher than in the endosperm but the total amount of amylase in the embryo is much less than in the endosperm. Although the embryo of sorghum is a minor contributor to the total amylase, it contributes more thsn does the embryo of barley to barley malt. The ratio of α- to β-amylase in the embryo differs from that found in the endosperm. In Short Red kaffircorn, a common malting variety, the embryo contained ii significantly lower percentage of αamylase than the endosperm. The opposite was found with the Birdproof and Sugar Drip varieties, the embryo being the richer in αamylase.     

Chromatography of alpha-, beta- and gamma-Cyclodextrin on Dextran Gel Columns

The chromatographic behaviour of α-, β- and γ-cyclodextrin on strongly cross-linked dextran gels was found very characteristic. Their elution sequence (1st γ-, 2nd α-, 3rd β-CD) is identical with the sequence of their decreasing solubility. The retention of α- and β-cyclodextrin depends significantly from the temperature, but does not depend in a measurable extent in the case of γ-cyclodextrin. An adsorption effect is dominating in the first two cases.     

Comparison of the distribution and toxicity of alpha-, beta-, and gamma-hexachlorocyclohexane (HCH) following 30 days of administration to rats

Administration of 1000 ppm alpha-HCH, 600 ppm beta-HCH and greater than or equal to 125 ppm gamma-HCH to rats caused a growth retardation. alpha-HCH and beta-HCH led to livermass enlargement. beta-HCH caused a decrease of absolute brain-mass. In case of alpha-HCH and gamma-HCH fat tissue, kidneys and adrenals had a high burden in residues. Fat tissue and adrenals had high residues of beta-HCH. The level of HCH-residues during the test period was gamma much less than beta less than alpha. The results are discussed taking into account the contradictory knowledge from literature.     

Spatial distribution and temporal variability of arsenic in irrigated rice fields in Bangladesh. 1. Irrigation water

Around 38% of the area of Bangladesh is irrigated with groundwater to grow dry season crops, most importantly boro rice. Due to high As concentrations in many groundwaters, over 1000 tons of As are thus transferred to arable soils each year, creating a potential risk for future food production. We studied the reactions and changing speciation of As, Fe, P, and other elements in initially anoxic water during and after irrigation and the resulting spatial distribution of As input to paddy soils near Sreenagar (Munshiganj), 30 km south of Dhaka, in January and April 2005 and February 2006. The irrigation water had a constant concentration of 397 +/- 7 microg L(-1) As (approximately 84% As(III)), 11 +/- 0.1 mg L(-1) Fe, and 2 +/- 0.1 mg L(-1) P. During the fast flow along the longest irrigation channel (152 m) As, Fe, and P speciation changed, but total concentrations did not decrease significantly, indicating that As input to fields was independent of the length of the irrigation channels. In contrast, during slow water flow across the fields, As, Fe, and P concentrations decreased strongly with increasing distance from the water inlet, due to formation and settling of As- and P-bearing Fe aggregates and by adsorption to soil minerals. Total As concentrations in field water were approximately 3 times higher close to the inlet than in the opposite field corner shortly after irrigation, and decreased to below 35 microg L(-1) over the next 72 h. The laterally heterogeneous transfer of As, Fe, and P from irrigation waterto soil has important consequences for their distribution in irrigated fields and needs to be considered in sampling and in assessing the dynamics and mass balances of As fluxes among irrigation water, soil, and floodwater.     

Spatial and seasonal variations of Hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) in the Arctic atmosphere

Weekly high-volume air samples were collected between 2000 and 2003 at six Arctic sites, i.e., Alert, Kinngait, and Little Fox Lake (LFL) in Canada, Point Barrow in Alaska, Valkarkai in Russia, and Zeppelin in Norway. Hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) were quantified in all samples. Comparison showed that alpha-HCH and HCB were homogeneously distributed in the circumpolar atmosphere and uniform throughout the seasons. However, significantly higher atmospheric concentrations of alpha-HCH and HCB and strongertemperature dependence of alpha-HCH and gamma-HCH were found at LFL in Yukon (YK), which is unique among the sites by virtue of its high altitude and low latitude, resulting in higher precipitation rates and summer temperatures. Strong temperature dependence of alpha- and gamma-HCH at this location suggests that secondary emissions, i.e., re-evaporation from surfaces, were more important at this site than others. It is hypothesized that a higher precipitation rate at LFL facilitated the transfer of alpha-HCH from the atmosphere to surface media when technical HCH was still in use worldwide. On the other hand, higher temperature at LFL enhanced reevaporation to the atmosphere after the global ban of technical HCH. In contrast to alpha-HCH and HCB, larger spatial and seasonal differences were seen for gamma-HCH (a currently used pesticide), which likely reflect the influence of different primary contaminant sources on different Arctic locations. Fugacity ratios suggest a net deposition potential of HCB from air to seawater, whereas seawater/air exchange direction of alpha-HCH varies in the circumpolar environment.     

Enhanced biodegradation of beta- and delta-hexachlorocyclohexane in the presence of alpha- and gamma-isomers in contaminated soils

The chlorinated insecticide hexachlorocyclohexane (HCH) has been used extensively in the past, and contaminated sites are present throughout the world. Toward their bioremediation, we isolated a bacterium Pseudomonas aeruginosa ITRC-5 that mediates the degradation of all the four major isomers of HCH under aerobic conditions, both in liquid-culture and contaminated soils. In liquid-culture, the degradation of alpha- and gamma-HCH is rapid and is accompanied with the release of 5.6 micromole chloride ions and 4.1 micromole CO2 micromole(-1) HCH-isomer. The degradation of beta- and delta-isomers is slow, accompanied with the release of 0.9 micromole chloride ions micromole(-1) HCH-isomer, and results in a transient metabolite 2,3,4,5,6-pentachlorocyclohexan-1-ol. The strain ITRC-5 also mediates the degradation of alpha-, beta-, gamma-, and delta-isomers in contaminated soils, where degradation of otherwise persistent beta- and delta-HCH is enhanced severalfold in the presence of alpha- or gamma-HCH. The degradation of soil-applied beta- and delta-HCH under aerobic conditions has not been reported earlier. The isolate ITRC-5 therefore demonstrates potential for the bioremediation of HCH-wastes and contaminated soils.     

Differential Inhibitory Effect of alpha-, beta-, gamma-, and delta-Tocopherols on the Metal-Induced Oxidation of Cholesterol in Unilamellar Phospholipid-Cholesterol Liposomes

ABSTRACT: Cholesterol oxidation products (COPs) are present in biological tissues and in foods. The inhibitory effect of antioxidants, such as tocopherols, on COPs formation has been only partially investigated. The antioxidant effect of dl alpha-, dl beta-, dl gamma-, and dl-delta tocopherol on the metal-induced oxidation of phosphatidylcholine (PC): cholesterol liposomes was assayed. Formation during liposome oxidation of six different COPs was monitored by gas chromatography. dl alpha-, and dl gamma-tocopherol show good inhibitory effect against PC-fatty acid oxidation and also on COPs formation. dl delta-Tocopherol is less effective than the alpha-and gamma-homologous, beta-tocopherol being unable to prevent PC and cholesterol oxidation. dl alpha-, and dl gamma-Tocopherol are more effective to prevent the oxidation of the lateral chain of cholesterol molecule. At the highest tocopherol concentration assayed, dl alpha-tocopherol shows prooxidant effect, enhancing liposomal oxidation and COPs formation. It is concluded that the tocopherols assayed can inhibit cholesterol oxidation but to a different degree.     

Levels and distribution of polybrominated diphenyl ethers in water, surface sediments, and bivalves from the San Francisco Estuary

Polybrominated diphenyl ethers (PBDEs) were found in water, surface sediments, and bivalve samples that were collected from the San Francisco Estuary in 2002. sigmaPBDE concentrations in water samples ranged from 3 to 513 pg/ L, with the highest concentrations found in the Lower South Bay (range 103-513 pg/L) region, which receives approximately 26% of the Estuary's wastewater treatment plant effluents. The sigmaPBDEs in sediments ranged from below detection limits to 212 ng/g dry wt, with the highest concentration found at a South Bay station (212 ng/g dry wt), which was up to 3 orders of magnitude higher than other stations. The sigmaPBDE concentrations ranged from 9 to 64 ng/g dry wt in oysters (Crassostrea gigas), from 13 to 47 ng/g dry wt in mussels (Mytilus californianus), and from 85 to 106 ng/g dry wt in clams (Corbicula fluminea). Only three PBDE congeners were detected in bivalves, BDE-47, BDE-99, and BOE-100; these are the most bioaccumulative congeners from the commercial Penta-BDE mixture.     

Anthropogenic Gd in surface water,drainage system,and the water supply of the city of Prague,Czech Republic

The anthropogenic Gd (Gdant) loads and fluxes of surface- and groundwaters, and of effluents from sewage treatment plants of Prague and its surroundings, have been determined. While passing Prague the Gdant load of the Vltava river increases from 4.5 to 19.2 nmol/m3, which is caused by the effluents of the central sewage treatment plant with a 6 day average of 250 nmol/m3. The Berounka river with its enhanced content doubles the Gdant flux of the Vltava river before entering Prague. All minor creeks draining Prague add less than 3% of the Gdant load in the Vltava river downstream of Prague. The 11-days average of the amount of the administered Gd complexes of the gadopentetic acid (Gd-DTPA), gadobenic acid, and other compounds in Prague's hospitals (22 g-Gdant/d) exceeds the 6 days average of 15 g-Gdant/d in the effluent of the central sewage treatment plant. This strongly indicates uncontrolled losses of sewage from sewers to the groundwater.     

GIS-based system for surface water risk assessment of agricultural chemicals. 1. Methodological approach

A methodology to develop a GIS-based system for the surface water risk assessment of agricultural chemicals is described. It is based on the integration of relational and spatial databases, GIS incorporating raster and vector, mass balance models, and pesticide risks indicators. Surface water pollution was modeled by taking into account two main processes: the load due to drift and the load due to a rainfall-runoff event. The former is immediately consequent to pesticide application; the second occurs a short period afterward. Thus two distinct PEC (predicted environmental concentration) values were estimated, differing in time. A pilot approach was applied to the herbicide alachlor on corn in Lombardia region (northern Italy) and represents the first stage of a wider project. Although the resultant alachlor PEC and risk maps represent a static image of a worst-case simulation, the main objective was to provide information for the territory with respect to relative risks at the watershed level, which is important in managing risks to the aquatic environment. The driving forces and spatial variability of the above-mentioned processes were investigated to improve knowledge about the territory and to indicate the need for more detailed site-specific studies.     

Mutations in Fks1p affect the cell wall content of beta-1,3- and beta-1,6-glucan in Saccharomyces cerevisiae

Fks1p and Fks2p are related proteins thought to be catalytic subunits of the beta-1,3-glucan synthase. Analysis of fks1 delta mutants showed a partial K1 killer toxin-resistant phenotype and a 30% reduction in alkali-soluble beta-1,3-glucan that was accompanied by a modest reduction in beta-1,6-glucan. The gas1 delta mutant lacking a 1,3-beta-glucanosyltransferase displayed a similar reduction in alkali-soluble beta-1,3-glucan but did not share the beta-1,6-glucan defect, indicating that beta-1,6-glucan reduction is not a general phenotype among beta-1,3-glucan biosynthetic mutants. Overexpression of FKS2 suppressed the killer toxin phenotype of fks1 delta mutants, implicating Fks2p in the biosynthesis of the residual beta-1,6-glucan present in fks1 delta cells. In addition, eight out of 12 fks1ts fks2 delta mutants had altered beta-glucan levels at the permissive temperature: the partial killer resistant FKS1F1258Y N1520D allele was severely affected in both polymers and displayed a 55% reduction in beta-1,6-glucan, while the in vitro hyperactive allele FKS1T605I M761T increased both beta-glucan levels. These beta-1,6-glucan phenotypes may be due to altered availability of, and structural changes in, the beta-1,3-glucan polymer, which might serve as a beta-1,6-glucan acceptor at the cell surface. Alternatively, Fks1p and Fks2p could actively participate in the biosynthesis of both polymers as beta-glucan transporters. We analysed Fks1p and Fks2p in beta-1,6-glucan deficient mutants and found that they were mislocalized and that the mutants had reduced in vitro glucan synthase activity, possibly contributing to the observed beta-1,6-glucan defects.     

Atmospheric Hexachlorocyclohexanes in the North Pacific Ocean and the adjacent Arctic region: spatial patterns, chiral signatures, and sea-air exchanges

During the 2003 Chinese Arctic Research Expedition (CHINARE2003) from the Bohai Sea to the high Arctic (37 degrees N to 80 degrees N) aboard the icebreaker Xuelong (Snow Dragon), air samples were collected for the analysis of hexachlorocyclohexanes (HCHs) in the North Pacific Ocean and adjacent Arctic region. The sigma HCHs (alpha-HCH + gamma-HCH) ranged from 2.3 to 95.1 pg/m3 with the highest levels observed in Far East Asia (32.5 pg/m3), followed by the North Pacific Ocean (17.0 pg/m3) and the Arctic (7.3 pg/ m3). Compared to previous studies in the same areas in 1990s, our measurements were approximately 1 order of magnitude lower. Because of disproportionate chemical reduction and physical fractioning during long-range transport, the ratios of alpha-HCH to gamma-HCH (alpha/gamma-HCH) showed a significant increasing trend from low to high latitudes, suggesting thatthe alpha/gamma-HCH range of 4-7 could not be used to identify sources of technical HCHs especially in remote areas. The ratios of (+)-alpha-HCH to the sum of (+)-alpha-HCH and (-)-alpha-HCH were on average much more biased from 0.5 compared to previous observations in mid-1990s, indicating the exchange of atmospheric alpha-HCH with those in the oceans, where (+)-alpha-HCH was selectively depleted in biological degradation processes. Estimated fugacity ratios based on available data for both alpha-HCH and gamma-HCH further implied their net volatilization from seawater to air in the Arctic Ocean.     

Characterization of equine cDNA sequences for alphaS1-, beta- and kappa-casein

Here we report the entire cDNA sequences for equine alphaS1-, beta- and kappa-casein. Based on interspecies comparison, nine exons were found in equine beta-casein and five in kappa-casein. In equine alphaS1-casein cDNA the exon 5 was missing, which resulted in the total of 18 exons instead of 19 theoretically possible exons in alphaS1-casein cDNA. Comparison of DNA sequences representing exon 5 in other species with corresponding equine genomic region confirmed the presence of cryptic exon in horse genomic DNA. Equine alphaS1-casein mRNA was present in three forms in the lactating mammary gland and we showed that the two shorter forms were produced by skipping either the exon 8 or exon 15. In horse, as in some other mammals, beta- and kappa-casein are considerably more conserved (sequence identity 53% to 59% and 57% to 67%, respectively) than alphaS1-casein which appears as the most variable casein among species (sequence identity 40% to 54%). Interestingly, horse caseins resemble human much more than bovine caseins which may also explain the high dietetic value of mares' milk.     

Hexachlorocyclohexanes and endosulfans in urban, rural, and high altitude air samples in the Fraser Valley, British Columbia: evidence for trans-Pacific transport

High-volume air samples collected over the period Aug. 14-30, 2001, in the Lower Fraser Valley, BC, Canada, were used to assess urban/rural differences of organochlorine pesticides (OCPs) for ground level samples and to attempt to directly measure events of trans-Pacific inputs through the mid-troposphere. Hexachlorocyclohexanes (alpha- and gamma-isomers; 2-25 pg m(-3)) and endosulfan1 and -2 (5-150 pg m(-3)) were detected in all ground level samples. Seven air samples were collected during mid-troposphere flights (approximately 4400 m altitude) over the Lower Fraser Valley. These flights occurred concurrently with ground level sampling. Trajectory analysis identified three events of substantial mid-troposphere, trans-Pacific flow where 10-day back trajectories stemmed from potential source regions in Asia. These events were also characterized by higher air concentrations of alpha-HCH at 4400 m as compared to the ground level stations. This represents the first event-based, aircraft measurement of advection inputs of OCPs in the mid-troposphere of the west coast of North America.     

Determination of total water and surface water in sugars

A clear distinction between differently bound water fractions by drying techniques is usually not possible. The Karl Fischer titration was used to achieve such a differentiation. As this technique is based on a chemical reaction, water is only determined when it comes into direct contact with the reagents. Surface water can therefore be detected easily. To limit the determination to this fraction, dissolution of the sample must be avoided. If, on the contrary, the total water is to be determined, the sample must either be dissolved completely or measures must be taken to liberate the water from the sample matrix. The aim of this work was to find titration parameters and working conditions that allow the distinction between the total water content and the surface water of sugars.     

双重净化-气相色谱法同时测定蛋及蛋制品中六六六、滴滴涕和指示性多氯联苯

建立同时测定蛋及蛋制品中六六六、滴滴涕和指示性多氯联苯残留量的双重净化-气相色谱法。样品经乙腈提取,浓硫酸和焙烧型水滑石双重净化后采用气相色谱分析和外标法定量。结果表明：与传统的磺化法相比,采用浓硫酸和焙烧型水滑石双重净化的效果更好,干扰物质少,且目标物提取更充分。在10～200 μg/L的添加水平内4 种六六六、2 种滴滴涕和7 种指示性多氯联苯的线性关系良好,相关系数均大于0.999。方法的检出限（RSN=3）范围为1.12～3.89 μg/kg,定量限（RSN=10）范围为3.73～12.97 μg/kg。添加10、20、100 μg/kg 3 个水平的4 种六六六、2 种滴滴涕和7 种指示性多氯联苯于鸡蛋液、咸蛋及皮蛋空白样品中,加标回收率范围为78.04%～105.05%,相对标准偏差范围为1.28%～7.55%。该方法操作简便快速、准确、灵敏,适用于蛋及蛋制品中六六六、滴滴涕和指示性多氯联苯残留量的快速测定。