选择性化学萃取对自然水体生物膜上微生物的影响

用平板计数法、显微镜直接计数法及培养法分别研究了选择性萃取剂对自然水体生物膜上细菌、原生动物和藻类的影响.结果表明,随着选择性萃取剂萃取能力的增强,生物膜上存活下来的微生物数量呈减少趋势.经001 mol·L^-1 NH₂OH·HCl+0.01 mol·L^-1 HNO₃、0.4 mol·L^-1 Na₂S₂O₄ (pH 6.0)和0.2 mol·L^-1草酸氨(pH 4.0)萃取后存活的微生物总量分别下降到原膜的27.6%、14.1%和0.01%;经15% HNO₃萃取后,膜上只有极少数的细菌存活;而经H₂O₂/HNO₃萃取后则无细菌存活、原生动物和藻类存活,说明选择性化学萃取剂的使用影响生物膜的活性.比较萃取前后生物膜吸附痕量重金属的能力发现,随着生物膜上微生物数量的减少,生物膜吸附痕量重金属的能力逐渐降低.     

Phytostabilization potential of Jatropha curcas L. in polymetallic acid mine tailings

Greenhouse pot experiments were conducted to determine the growth response, metal tolerance, and phytostabilization potential of Jatropha curcas L The plants were grown on different degrees of multi-metal contaminated acid mine soils (T0, control; T1, moderately and T2, highly contaminated soils) with or without limestone amendments. The order of metal accumulation in J. curcas was roots>stems>leaves. The higher tolerance index (>90%) with no phytotoxic symptoms and growth reduction in T1 showed that this plant has the ability to tolerate polymetallic acid mine tailings. Further, various enzymatic and non-enzymatic antioxidants also actively involved in metal defense mechanism in J. curcas. On the other hand, to alleviate the predominant phytoavailable toxic metals such as Al, Cu, and Pb, different rates (0.1, 0.25, 0.50, and 1%) of limestone amendments were added in both T1 and T2 soils. The growth performance of J. curcas was improved due to the increase in soil pH and decrease in phytoavailable soil A1 (95%), Zn (approximately 75%), and Cu (approximately 65%) contents at 0.50% of lime addition. Based on the inherent tolerance ability of J. curcas in existing adverse environmental conditions without liming, it could be used as a suitable candidate for phytostabilization in acid mine tailings.     

Assessment of different sample processing procedures applied to the determination of melatonin in plants

Introduction –  Melatonin, an indoleamine well known in vertebrates and structurally related to other important substances such as tryptophan or indole‐3‐acetic acid, is also present in the plant kingdom although its specific function(s) remain to be established. The emerging field of melatonin studies in plants has progressed very slowly, mainly due to the problems associated with melatonin quantification in plants. Objective –  Two commonly used procedures for plant samples are compared. The analytical characteristics of both procedures are quantitatively presented using different solvents and small amounts of fresh biological material, and the respective recovery rates and quantitative limits are presented. Some improvements are suggested. Methodology –  Two different sample extraction procedures were compared: a direct‐sample extraction (DSE) and a homogenised‐ sample extraction (HSE). Melatonin was then determined in the respective plant samples by HPLC with fluorescence detection. Results –  Using the DSE procedure, more than 94% melatonin was recovered from standard solutions, whereas levels higher than 93% were recovered from the spiked plant samples, with little difference between ethyl acetate and chloroform extractions. In the case of HSE, the recoveries of melatonin were approximately half and never higher than 55%. The ultrasonic treatment proposed in the DSE procedure showed different levels of efficiency (2–20%), depending on the sample. Conclusion –  This study has established that, with the direct sample extraction procedure, higher recovery rates are obtained both in standard solutions and in plant samples. The straightforwardness and reproducibility of the extraction procedure is accompanied by the high sensitivity obtained with fluorescence detection. Copyright © 2008 John Wiley & Sons, Ltd.     

Complexation of labile aluminium species by chelating resins Iontosorb--a new method for Al environmental risk assessment

The utilization of chelating ion-exchange by the method based on binding strength and kinetic discrimination for aluminium fractionation was studied. Two chelating cellulose resins, Iontosorb Oxin (IO) and Iontosorb Salicyl (IS), were used for the determination of quickly reacting labile aluminium species. The possibilities of aluminium fractionation on these chelating resins were investigated by a solid phase extraction technique. The study of the pH (2.5-6.0) influence on the Al complexation by both resins indicates that at low pH the IS has lower sorption capacity but better adsorptive kinetic properties than IO. The optimal resin complexation time for reactive Al species was experimentally found after aluminium sorption study at pH 4.0 in synthetic solutions containing some inorganic and organic ligands, which simulate the composition of analysed acid soil and water samples. The negative influence of sulphate and iron on the Al complexation by IS resin was found and investigated. The flame atomic absorption spectrometry was used for the aluminium quantification.     

Extraction and characterization of pectic substances from pulp of grape berries

Pectic substances were successively extracted from the alcohol-insoluble residue (AIR) of the pulp of grape berries, by water (WSP), oxalate (OXP), hot dilute HCl (HP) and cold dilute NaOH (OHP). Pectins (WSP, OXP, HP) were purified by ion-exchange chromatography (DEAE-Sephacel) or precipitation with cupric ions (OHP). Total pectic substances represent 20·8% (w/w) of the AIR, WSP and HP being the main components (6% and 12% of the AIR, respectively). An alternative to oxalate extraction of the water-insoluble pectin was extraction with NaCl solutions of increasing concentrations, which had released small amounts of pectins. Each of the fractions contained mainly galacturonic acid, arabinose and galactose, lower amounts of rhamnose and xylose, and minor amounts of glucose and mannose. Ion-exchange chromatography was performed on DEAE-Sephacel, M_w distribution was checked by gel permeation on Sepharose CL-2B, and M_v was determined as well as degrees of methylesterification (DM), acetylation (DA), and protein content.     

HCl causes less intracellular acidification in Necturus gastric mucosa surface epithelial cells than other acids

Luminal acid causes intracellular acidification in the gastric epithelium, but the mechanism by which H(+) enters surface cells remains obscure. This study addressed the problem by assessing how different acids affect intracellular pH in gastric surface cells. Isolated Necturus maculosus antral mucosa was exposed to HCl, HNO(3), H(2)SO(4), and H(3)PO(4) at pH 2.30. Intracellular pH was measured with microelectrodes. The physicochemical interaction of a synthetic model of gastric phospholipids with the different acids was studied using Langmuir film balance. Exposure to luminal HNO(3), H(2)SO(4), or H(3)PO(4) caused significantly larger intracellular acidification than exposure to HCl. The degree of acidification was not dependent on the valence or nature of the anionic counterion of the acid but significantly correlated with the amount of molecular acid. By Langmuir film balance, subphases acidified with HNO(3), H(2)SO(4), or H(3)PO(4) caused more close packing of phospholipid molecules than those acidified with HCl, possibly allowing hydrogen bonding between head groups to facilitate H(+) movement across the phospholipid membrane. HCl causes significantly less intracellular acidification in gastric epithelium than HNO(3), H(2)SO(4), or H(3)PO(4). This may be caused by the lower amount of molecular HCl in solution and possible hydrogen bonding between the head groups of phospholipid molecules and the other acids.     

The extraction of leukotrienes (LTC4, LTD4, and LTE4) from tissue fluids: the metabolism of these mediators during IgE-dependent hypersensitivity reactions in lung

The metabolites of arachidonic acid known as the leukotrienes are a class of lipid mediators which have potent and diverse biological effects in pulmonary tissue. Leukotrienes C, D, and E (LTC4, LTD4, and LTE4) are known to be principal mediators of immunoglobulin E (IgE)-mediated hypersensitivity reactions in lung tissue. It is therefore important to develop reliable and quantitative isolation techniques for estimating levels of these mediators in tissue. In this study, LTC4, LTD4, and LTE4 were separated from other arachidonate metabolites by organic extraction procedures. 5-Hydroxyeicosatetraeonic acid and leukotriene B4 extract efficiently into the organic layer of aqueous:ether or aqueous:chloroform extractions, whereas arachidonate metabolites containing conjugated peptides (e.g., LTC4, LTD4, and LTE4) failed to extract into these organic solvents. An extraction step was therefore developed that affords quantitative extraction of LTC4, LTD4, and LTE4 into the organic phase of an isopropanol:ether:H2O mixture. This step is the key for a two-step extraction method that isolates histamine, LTC4, LTD4, and LTE4 with a recovery of 100, 85, 75, and 57%, respectively. One advantage of this separation procedure for obtaining these mediators by organic extraction is an ability to expediently process many samples. Furthermore, the leukotriene content of extracted samples can be analyzed using the guinea pig ileum bioassay without interference from vasoamines or platelet-activating factor. These later substances are eliminated from leukotriene-enriched fractions by this extraction process. When histamine and LTC4 were added to supernatant fluids recovered from isolated lung tissue, they were quantitatively recovered using this extraction method.(ABSTRACT TRUNCATED AT 250 WORDS)     

Possible method of aluminium speciation in forest soils

Labile Al forms and species can be a threat in acid soils due to their potential toxicity to plants. However, there is no universally accepted extraction method. Several extraction reagents for Al release from soil have been tested. KCl (0.5 or 1 M) is recommended for extraction of exchangeable Al, while 0.5 or 0.3 M CuCl(2) is suggested for extraction of 'weakly organically bound Al'. Both 0.1 and 0.05 M Na(4)P(2)O(7) are shown to be suitable for the extraction of 'total organically bound Al'. These extractions are relatively simple, robust, and applicable to different soils and soil horizons. In the second part of the paper, detailed speciation of exchangeable soil Al by means of an HPLC instrument equipped with an ion column (IC) is presented. An experimental set-up is described and tested on a set of samples. Interpretation of the speciation results is proposed, based on the separation of Al ions and Al complexes according to their charge. Speciation is shown to be dependent mainly on soil pH and organic matter quality. A general scheme of Al fractionation and speciation in soil is proposed.     

Studies on chemical modification of thionucleosides in the transfer ribonucleic acid of Escherichia coli

(35)S-labelled tRNA from Escherichia coli was treated with chemical reagents such as CNBr, H(2)O(2), NH(2)OH, I(2), HNO(2), KMnO(4) and NaIO(4), under mild conditions where the four major bases were not affected. Gel filtration of the treated tRNA showed desulphurization to various extents, depending on the nature of the reagent. The treated samples after conversion into nucleosides were chromatographed on a phosphocellulose column. NH(2)OH, I(2) and NaIO(4) reacted with all the four thionucleosides of E. coli tRNA, 4-thiouridine (s(4)U), 5-methylaminomethyl-2-thiouridine (mnm(5)s(2)U), 2-thiocytidine (s(2)C) and 2-methylthio-N(6)-isopentenyladenosine (ms(2)i(6)A), to various extents. CNBr, HNO(2) and NaHSO(3) reacted with s(4)U, mnm(5)s(2)U and s(2)C, but not with ms(2)i(6)A. KMnO(4) and H(2)O(2) were also found to react extensively with thionucleosides in tRNA. Iodine oxidation of (35)S-labelled tRNA showed that only 6% of the sulphur was involved in disulphide formation. Desulphurization of E. coli tRNA with CNBr resulted in marked loss of acceptor activities for glutamic acid, glutamine and lysine. Acceptor activities for alanine, arginine, glycine, isoleucine, methionine, phenylalanine, serine, tyrosine and valine were also affected, but to a lesser extent. Five other amino acids tested were almost unaffected. These results indicate the fate of thionucleosides in tRNA when subjected to various chemical reactions and the involvement of sulphur in aminoacyl-tRNA synthetase recognition of some tRNA species of E. coli.     

氮、磷、钾肥配施对桂花品种'金玉台阁'开花性状及叶片中叶绿素和营养元素含量的影响

以桂花品种'金玉台阁'(Osmanthus fragrans'Jinyu Taige')盆栽苗为供试材料,采用"3414"肥料效应试验设计方案,研究了不同单株施用量CO(NH2)2(0.0、1.0、2.0和3.0 g)、NH4H2PO4(0.0、1.5、3.0和4.5 g)和KCl(0.0、0.5、1.0、1.5 g)对秋冬生长期(2014年10月至2015年2月)'金玉台阁'开花性状及叶片中叶绿素和营养元素的影响进行了比较和分析,并筛选出适宜的氮、磷、钾肥施用量.结果表明:与CK〔CO(NH2)2、NH4H2PO4和KCl的单株施用量均为0.0 g〕组相比,各氮、磷、钾肥配施处理组'金玉台阁'的单株产花量、花瓣相对含水量、花径以及叶片中叶绿素、全氮、全磷和全钾的含量总体上显著升高.CO(NH2)2单株施用量对'金玉台阁'单株产花量、叶片中叶绿素含量和全氮含量的影响最大,NH4H2PO4单株施用量对这3个指标的影响次之;NH4H2PO4单株施用量对'金玉台阁'叶片中全磷含量的影响最大;KCl单株施用量对'金玉台阁'花瓣相对含水量、花径及叶片中全钾含量的影响最大.在秋冬生长期内叶片中叶绿素含量呈先降低后升高的趋势,均在12月份降至最低值.通过建立'金玉台阁'单株产花量(y)与CO(NH2)2、NH4 H2 PO4和KCl的单株施用量(分别为xN、xP和xK)间的肥料效应模型,得到的三元二次肥料效应模型为y=1.2027+0.7561×xN+0.2632×xP+0.4590×xK-0.2761×xN2-0.1201×xP2-0.5007×xK2+0.1901×xN×xP-0.0960×xN×xK+0.1185×xP×xK.以单株产花量为目标,'金玉台阁'的CO(NH2)2、NH4 H2 PO4和KCl的最佳单株施用量分别为2.58、3.56和0.86 g.     

Generation of nitroxyl by heme protein-mediated peroxidation of hydroxylamine but not N-hydroxy-L-arginine

The chemical reactivity, toxicology, and pharmacological responses to nitroxyl (HNO) are often distinctly different from those of nitric oxide (NO). The discovery that HNO donors may have pharmacological utility for treatment of cardiovascular disorders such as heart failure and ischemia reperfusion has led to increased speculation of potential endogenous pathways for HNO biosynthesis. Here, the ability of heme proteins to utilize H(2)O(2) to oxidize hydroxylamine (NH(2)OH) or N-hydroxy-L-arginine (NOHA) to HNO was examined. Formation of HNO was evaluated with a recently developed selective assay in which the reaction products in the presence of reduced glutathione (GSH) were quantified by HPLC. Release of HNO from the heme pocket was indicated by formation of sulfinamide (GS(O)NH(2)), while the yields of nitrite and nitrate signified the degree of intramolecular recombination of HNO with the heme. Formation of GS(O)NH(2) was observed upon oxidation of NH(2)OH, whereas NOHA, the primary intermediate in oxidation of L-arginine by NO synthase, was apparently resistant to oxidation by the heme proteins utilized. In the presence of NH(2)OH, the highest yields of GS(O)NH(2) were observed with proteins in which the heme was coordinated to a histidine (horseradish peroxidase, lactoperoxidase, myeloperoxidase, myoglobin, and hemoglobin) in contrast to a tyrosine (catalase) or cysteine (cytochrome P450). That peroxidation of NH(2)OH by horseradish peroxidase produced free HNO, which was able to affect intracellular targets, was verified by conversion of 4,5-diaminofluorescein to the corresponding fluorophore within intact cells.     

Determination of trace amounts of total dissolved cationic aluminium species in environmental samples by solid phase extraction using nanometer-sized titanium dioxide and atomic spectrometry techniques

Nanometer-sized titanium dioxide was used as a solid-phase extractant for the separation and preconcentration of trace amounts of Al(III) prior to its determination by electrothermal atomic absorption spectrometry (ET AAS) and inductively coupled plasma optical emission spectrometry (ICP OES). The optimal conditions for the proposed solid phase extraction (SPE; 50 mg TiO₂, 10 min extraction time, pH 6.0, HCl and HNO₃ as eluents) and ET AAS measurement (1500 °C pyrolysis and 2600 °C atomization temperatures, Mg(NO₃)₂ as matrix modifier) were obtained. The adsorption capacity of TiO₂ was 4.1 mg Al g⁻¹ TiO₂. Two modes of the proposed procedure were compared, (I) batch and elution mode with the elution of Al from TiO₂ phase by nitric or hydrochloric acid, and (II) batch and slurry mode (without elution) with the direct TiO₂ phase-slurry sampling. Finally, the batch and slurry mode of nanometer-sized TiO₂ SPE with slurry ET AAS detection and quantification was preferred and used for the determination of trace amounts of total dissolved cationic Al species in synthetic and natural water samples. The method accuracy was checked by the analysis of lake water CRM TMDA-61 and by the technique of analyte addition (sample spiking). Under the optimal conditions, the calibration curve for batch and slurry TiO₂ SPE with a 10-fold preconcentration was linear up to 40 μg L⁻¹ Al. The limit of detection (LOD) and the limit of quantification (LOQ) was 0.11 μg L⁻¹ Al and 0.35 μg L⁻¹ Al, respectively, with a preconcentration factor of 20 and a relative standard deviation (RSD) lower than 5%.     

Overexpression of Malate Dehydrogenase in Transgenic Alfalfa Enhances Organic Acid Synthesis and Confers Tolerance to Aluminum

Al toxicity is a severe impediment to production of many crops in acid soil. Toxicity can be reduced through lime application to raise soil pH, however this amendment does not remedy subsoil acidity, and liming may not always be practical or cost-effective. Addition of organic acids to plant nutrient solutions alleviates phytotoxic Al effects, presumably by chelating Al and rendering it less toxic. In an effort to increase organic acid secretion and thereby enhance Al tolerance in alfalfa (Medicago sativa), we produced transgenic plants using nodule-enhanced forms of malate dehydrogenase and phosphoenolpyruvate carboxylase cDNAs under the control of the constitutive cauliflower mosaic virus 35S promoter. We report that a 1.6-fold increase in malate dehydrogenase enzyme specific activity in root tips of selected transgenic alfalfa led to a 4.2-fold increase in root concentration as well as a 7.1-fold increase in root exudation of citrate, oxalate, malate, succinate, and acetate compared with untransformed control alfalfa plants. Overexpression of phosphoenolpyruvate carboxylase enzyme specific activity in transgenic alfalfa did not result in increased root exudation of organic acids. The degree of Al tolerance by transformed plants in hydroponic solutions and in naturally acid soil corresponded with their patterns of organic acid exudation and supports the concept that enhancing organic acid synthesis in plants may be an effective strategy to cope with soil acidity and Al toxicity.     

Direct analysis of abscisic acid in crude plant extracts by liquid chromatography--electrospray/tandem mass spectrometry

A new method, based on liquid chromatography--electrospray/tandem mass spectrometry, for the determination of abscisic acid (ABA), an essential plant hormone that regulates key metabolic pathways and responses to environmental cues, has been developed. Substantial changes in extraction procedures are also proposed. Data indicate that the organic solvents classically used as extraction buffers can be substituted by an aqueous solution, resulting in the same amounts of extracted ABA. The new method, which uses minute amounts of plant tissue, has an estimated limit of detection below 50 pmol ABA/g, and the sensitivity of the technique allows the analysis of ABA in crude plant extracts. Overall, this new rapid, sensitive and accurate procedure to determine ABA will allow analysis of multiple samples in a short time and represents a clear advantage in comparison with the conventional procedures involving many preparative steps and large amounts of plant tissue.     

Potential errors caused by roots in analyses of rhizosphere soil

Roots contain high concentrations of many elements, and have the potential to interfere with measurements of chemical change in rhizosphere soil. To assess potential interferences, maize (Zea mays L.) roots (free of soil) and soil (free of roots) were extracted separately with several extractants commonly used to assess the status of soil nutrients. The maize roots were grown within filter envelopes which prevented direct contact with soil, but permitted passage of mineral nutrients and water from the adjacent soil. Water, ammonium acetate (pH 7), DTPA (pH 7.3), Morgan's solution (pH 4.8), and dilute HCl were used as extractants. Most elements were released readily into soluble forms from roots killed by freezing to lyse the cells. Significantly lower amounts were extracted from fresh roots, with the greatest differences between fresh and killed roots for the extractants H₂O and DTPA, which were the mildest in terms of acidity and salt concentration. Extraction of P from the fresh roots by H₂O and HCL was particularly low. Contamination of rhizosphere samples with root materials would almost certainly prevent the accurate measurement of water-soluble P, K, Mn, Zn, Cu, and Na in the slightly alkaline soil used in this experiment. Large errors would be likely also for P, Mn, and Cu extracted by ammonium acetate. The DTPA extractant is normally used only for micronutrient metals or heavy metals, and the small amounts of these elements released by roots should not contribute to significant error. With Morgan's solution, errors would likely be large only for P. Dilute HCl is a reasonably strong extractant for many elements in soil, and major errors from roots contained in rhizosphere samples are unlikely. The relatively high probability of errors in extractions of soluble elements from rhizosphere soil is unfortunate, because these elements are among the most readily available to plants and the most likely to be altered by the normal activities of roots.     

Effects of acid pre-treatment on bio-hydrogen production and microbial communities during dark fermentation

Optimal conditions for acid pre-treatment were investigated for the enrichment of hydrogen-producing bacteria (HPB) in a mixed culture using three strong acids: HCl, HNO(3), and H2SO4 x HCl was selected as a suitable acid for the enrichment of HPB in the fermentation process. The volume of bio-hydrogen produced when the mixed culture was pre-treated using HCl at pH 2 was 3.2 times higher than that obtained without acid pre-treatment. Changes in the microbial community during acid pre-treatment were monitored using images obtained by the fluorescent in situ hybridization (FISH) method and the Live/Dead cell viability test. The tests clearly indicated that the Clostridium species of cluster I were the predominant strains involved in bio-H(2) fermentation, and could be selectively enriched by HCl pre-treatment.     

An Improved Semiquantitative Method for Elemental Analysis of Plants Using Inductive Coupled Plasma Mass Spectrometry

A semiquantitative ICP-MS method suitable for evaluating metal content in plants exposed to high metal concentrations is described. The methodology which has been tested using different plant reference material is able, in only a few minutes, to obtain qualitative and quantitative information from the sample. Recoveries close to 100% were obtained for more than half of the referenced elements with an RSD <10%, thus avoiding the generation of a calibration line for each of the elements to be analyzed. The use of multi-standards improves the results obtained with conventional standards by a factor of two. In these conditions the semiquantitative multi-elemental analysis is a valid alternative for most of the analyzed elements with the exception of Si, Al, and P which requires the use of a quantitative ICP-MS analysis for its determination. Two different digestion protocols were tested, with and without the addition of HF to the HNO(3)?+?H(2)O(2) extraction mixture. Similar results were obtained for poplar and bush reference materials using the HNO(3)?+?H(2)O(2) mixture. The addition of HF did not improve the recovery of different elements, in general, but is critical for the quantitative measurements of Al and Si as its presence allows results to be obtained with an RDS <5%.     

Concentrations,deposition, and effects of nitrogenous pollutants in selected California ecosystems

Atmospheric deposition of nitrogen (N) in California ecosystems is ecologically significant and highly variable, ranging from about 1 to 45 kg/ha/year. The lowest ambient concentrations and deposition values are found in the eastern and northern parts of the Sierra Nevada Mountains and the highest in parts of the San Bernardino and San Gabriel Mountains that are most exposed to the Los Angeles air pollution plume. In the Sierra Nevada Mountains, N is deposited mostly in precipitation, although dry deposition may also provide substantial amounts of N. On the western slopes of the Sierra Nevada, the majority of airborne N is in reduced forms as ammonia (NH3) and particulate ammonium (NH4+) from agricultural activities in the California Central Valley. In southern California, most of the N air pollution is in oxidized forms as nitrogen oxides (NOx), nitric acid (HNO3), and particulate nitrate (NO3-) resulting from fossil fuel combustion and subsequent complex photochemical reactions. In southern California, dry deposition of gases and particles provides most (up to 95%) of the atmospheric N to forests and other ecosystems. In the mixed-conifer forest zone, elevated deposition of N may initially benefit growth of vegetation, but chronic effects may be expressed as deterioration of forest health and sustainability. HNO3 vapor alone has a potential for toxic effects causing damage of foliar surfaces of pines and oaks. In addition, dry deposition of predominantly HNO3 has lead to changes in vegetation composition and contamination of ground- and stream water where terrestrial N loading is high. Long-term, complex interactions between N deposition and other environmental stresses such as elevated ozone (O3), drought, insect infestations, fire suppression, or intensive land management practices may affect water quality and sustainability of California forests and other ecosystems.     

Effects of acidification on mercury methylation, demethylation, and volatilization in sediments from an acid-susceptible lake

The effect of experimental acidification on mercury methylation, demethylation, and volatilization was examined in surficial sediment samples from a weakly buffered northern Wisconsin lake. All mercury transformations were measured with radioisotopic tracers. Acidification of sediment pH with H2SO4, HCl, or HNO3 significantly decreased 203Hg(II) methylation. Acidification of pH 6.1 (ambient) sediments to pH 4.5 with either H2SO4 or HCl inhibited methylation by over 65%. The decreased methylation was due to the increased hydrogen ion concentration because methylation was not affected by concentrations of Na2SO4 or NaCl equimolar to the amount of acid added. Inhibition of methylation was observed even after prolonged acidification of sediments to pH 5.0 for up to 74 days. Acidification of sediments to pH 5.5, 4.5, and 3.5 with HNO3 resulted in a near complete inhibition of methylation at each pH. Similarly, the addition of equimolar amounts of NaNO3 resulted in a near complete inhibition of methylation, indicating that the inhibition was due to the nitrate ion rather than to the acidity. Demethylation of methyl mercury was not affected by pHs between 8.0 and 4.4, but sharply decreased below pH 4.4. Volatilization of 203Hg(II) from surface sediments was less than 2% of methylation activity and was not significantly different from that in killed sediments. This study indicated that acidification of sediments inhibits mercury methylation and that the observed increase in the mercury burdens in fish from low pH lakes is not due to increased production of methylmercury in sediments.     

Effects of acidification on mercury methylation, demethylation, and volatilization in sediments from an acid-susceptible lake.

The effect of experimental acidification on mercury methylation, demethylation, and volatilization was examined in surficial sediment samples from a weakly buffered northern Wisconsin lake. All mercury transformations were measured with radioisotopic tracers. Acidification of sediment pH with H2SO4, HCl, or HNO3 significantly decreased 203Hg(II) methylation. Acidification of pH 6.1 (ambient) sediments to pH 4.5 with either H2SO4 or HCl inhibited methylation by over 65%. The decreased methylation was due to the increased hydrogen ion concentration because methylation was not affected by concentrations of Na2SO4 or NaCl equimolar to the amount of acid added. Inhibition of methylation was observed even after prolonged acidification of sediments to pH 5.0 for up to 74 days. Acidification of sediments to pH 5.5, 4.5, and 3.5 with HNO3 resulted in a near complete inhibition of methylation at each pH. Similarly, the addition of equimolar amounts of NaNO3 resulted in a near complete inhibition of methylation, indicating that the inhibition was due to the nitrate ion rather than to the acidity. Demethylation of methyl mercury was not affected by pHs between 8.0 and 4.4, but sharply decreased below pH 4.4. Volatilization of 203Hg(II) from surface sediments was less than 2% of methylation activity and was not significantly different from that in killed sediments. This study indicated that acidification of sediments inhibits mercury methylation and that the observed increase in the mercury burdens in fish from low pH lakes is not due to increased production of methylmercury in sediments.