Arsenic contamination of natural waters in San Juan and La Pampa, Argentina

Arsenic (As) speciation in surface and groundwater from two provinces in Argentina (San Juan and La Pampa) was investigated using solid phase extraction (SPE) cartridge methodology with comparison to total arsenic concentrations. A third province, Río Negro, was used as a control to the study. Strong cation exchange (SCX) and strong anion exchange (SAX) cartridges were utilised in series for the separation and preservation of arsenite (As^III), arsenate (As^V), monomethylarsonic acid (MA^V) and dimethylarsinic acid (DMA^V). Samples were collected from a range of water outlets (rivers/streams, wells, untreated domestic taps, well water treatment works) to assess the relationship between total arsenic and arsenic species, water type and water parameters (pH, conductivity and total dissolved solids, TDS). Analysis of the waters for arsenic (total and species) was performed by inductively coupled plasma mass spectrometry (ICP-MS) in collision cell mode. Total arsenic concentrations in the surface and groundwater from Encon and the San José de Jáchal region of San Juan (north-west Argentina within the Cuyo region) ranged from 9 to 357 μg l^?1 As. Groundwater from Eduardo Castex (EC) and Ingeniero Luiggi (LU) in La Pampa (central Argentina within the Chaco-Pampean Plain) ranged from 3 to 1326 μg l^?1 As. The pH range for the provinces of San Juan (7.2–9.7) and La Pampa (7.0–9.9) are in agreement with other published literature. The highest total arsenic concentrations were found in La Pampa well waters (both rural farms and pre-treated urban sources), particularly where there was high pH (typically > 8.2), conductivity (>2,600 μS cm^?1) and TDS (>1,400 mg l^?1). Reverse osmosis (RO) treatment of well waters in La Pampa for domestic drinking water in EC and LU significantly reduced total arsenic concentrations from a range of 216–224 μg l^?1 As to 0.3–0.8 μg l^?1 As. Arsenic species for both provinces were predominantly As^III and As^V. As^III and As^V concentrations in San Juan ranged from 4–138 μg l^?1 to <0.02–22 μg l^?1 for surface waters (in the San José de Jáchal region) and 23–346 μg l^?1 and 0.04–76 μg l^?1 for groundwater, respectively. This translates to a relative As^III abundance of 69–100% of the total arsenic in surface waters and 32–100% in groundwater. This is unexpected because it is typically thought that in oxidising conditions (surface waters), the dominant arsenic species is As^V. However, data from the SPE methodology suggests that As^III is the prevalent species in San Juan, indicating a greater influence from reductive processes. La Pampa groundwater had As^III and As^V concentrations of 5–1,332 μg l^?1 and 0.09–592 μg l^?1 for EC and 32–242 μg l^?1 and 30–277 μg l^?1 As for LU, respectively. Detectable levels of MA^V were reported in both provinces up to a concentration of 79 μg l^?1 (equating to up to 33% of the total arsenic). Previously published literature has focused primarily on the inorganic arsenic species, however this study highlights the potentially significant concentrations of organoarsenicals present in natural waters. The potential for separating and preserving individual arsenic species in the field to avoid transformation during transport to the laboratory, enabling an accurate assessment of in situ arsenic speciation in water supplies is discussed.     

丙烯酰胺对水环境中典型微藻的毒性效应

作为可疑致癌物,丙烯酰胺(acrylamide,AM)是目前各国政府和广大民众普遍关注的重要污染物.为探究AM对水体生物的毒性效应及可能存在的生态风险,本文以海洋微藻东海原甲藻(Prorocentrum donghaiense)和淡水微藻莱茵衣藻(Chlamydomonas reinhardtii)为研究对象,采用室内培养法,测定了不同暴露浓度的AM对2种微藻生长、形态和生理状态的影响.结果显示,AM对2种藻类生长均有显著的抑制作用(P0.05),96 h半抑制质量浓度(EC_(50))分别为22.79 mg·L~(-1)和161.8 mg·L~(-1);最高无抑制浓度(NOEC)分别为1.04 mg·L~(-1)和9.84 mg·L~(-1).不同微藻对AM胁迫的响应存在较大的差异性,与莱茵衣藻相比,东海原甲藻对AM更敏感.扫描电镜(SEM)和透射电镜(TEM)结果显示,当受到AM影响时,2种藻细胞严重变形,表现出塌陷、质壁分离、空泡数量增多和叶绿体片层结构少量断裂等现象;叶绿素含量和F_v/F_m(PSⅡ最大光化学量子产量)测试表明AM可以通过破坏微藻的光合系统而抑制光合作用.AM对东海原甲藻属于中毒性物质,对莱茵衣藻属于低毒性物质.     

Humic acids decrease the photodegradation of the sunscreen UV filter 2-phenylbenzimidazole-5-sulfonic acid in natural waters

The sunscreen UV filter 2-phenylbenzimidazole-5-sulfonic acid (PBSA) is an emerging pollutant recently detected in surface waters. PBSA is photolabile in pure water and sunscreen cream. PBSA photoinduces DNA damages. However, the photochemical behavior and environmental persistence of PBSA are not well known. Here, we studied the photochemical transformation of PBSA in sea and continental waters. Results show that photodegradation is dependent on water constituents. Whereas low concentrations of humic acids accelerate PBSA photodegradation slightly, high concentrations of humic acids inhibit the photodegradation. Colloidal organic matters of high molecular weights are the main water constituents inhibiting photodegradation. The estimated solar photolytic half-life of PBSA at environmental concentration levels ranged from 3?days from June to August to 35?days in December. Findings show that PBSA is not persistent in waters that are low in colloidal organic matters.     

Stimulation of phytoplankton production in coastal waters by natural rainfall inputs: Nutritional and trophic implications

Recent evaluations of estuarine and coastal nutrient budgets implicate atmospheric deposition as a potentially significant (20 to 30%) source of biologically available nitrogen. We examined the potential growth stimulating impact of atmospheric nitrogen loading (ANL), as local rainfall, in representative shallow, nitrogen limited North Carolina mesohaline estuarine and euhaline coastal Atlantic Ocean habitats. From July 1988 to December 1989, using in situ bioassays, we examined natural phytoplankton growth responses, as¹⁴CO₂ assimilation and chlorophylla production, to rain additions over a range of dilutions mimicking actual input levels. Rainfall at naturally occurring dilutions (0.5 to 5%) stimulated both¹⁴CO₂ assimilation and chlorophylla production, in most cases in a highly significant manner. Parallel nutrient enrichments consistently pointed to nitrogen as the growth stimulating nutrient source. Generally, more acidic rainfall led to greater magnitudes of growth stimulation, especially at lower dilutions. Nutrient analyses of local rainfall from May 1988 to January 1990 indicated an inverse relationship between pH and NO ₃ ^- content. There have been growing concerns regarding increasing coastal and estuarine eutrophication, including ecologically and economically devastating phytoplankton blooms bordering urban and industrial regions of North America, Europe, Japan, and Korea. It appears timely, if not essential, to consider atmospheric nutrient loading in the formulation and implementation of nutrient management strategies aimed at mitigating coastal eutrophication.     

自然水体生物膜有机组分对Cd2+的吸附特征

室内模拟研究了长春南湖水生物膜中有机组分即胞外聚合物、微生物非活性细胞和微生物活性细胞对Cd^2＋的吸附特征及其影响因素。结果表明：3种有机组分对Cd^2＋的吸附过程分为快速和慢速阶段，达到吸附平衡的时间分别为360、100和100min；Cd^2＋的吸附最均在pH为6h达到最佳；在实验所选温度范围内，胞外聚合物在30℃时对Cd^2＋的吸附量最大．而温度对Cd^2＋在微生物非活性细胞和活性细胞的影响不显著；Cd^2＋在3种有机组分上的吸附均符合Langmuir和Freundlish热力学方程，吸附能力为胞外聚合物〉微生物非活性细胞〉微生物活性细胞。在有Pb^2＋共存的条件下，Langmuir和Freundlish热力学方程仍然适合描述3种有机组分对Cd^2＋的热力学吸附过程，但Cd^2＋的吸附量和饱和吸附最均减小。     

Toxicity of tri- and penta-valent arsenic, alone and in combination, to the cladoceran Daphnia carinata: the influence of microbial transformation in natural waters

The acute toxicity of arsenic(III) and arsenic(V) alone and in combination to a cladoceran, Daphnia carinata, was studied in both cladoceran culture medium and natural water collected from a local suburban stream. As(III) was found to be more toxic than As(V) to Daphnia survival. The LC₅₀ values for As(III), As(V), and As(III) + As(V) were 0.554, 1.499, and 0.692 mg l⁻¹, respectively. Although various species of As, particularly As(III) and As(V) co-exist together in natural waters, the existing guidelines for water quality are based on individual As species. The results of this investigation suggest that As(III) and As(V) can interact either synergistically or additively resulting in an increase in the overall toxicity of the mixture compared to individual As species. Also, indigenous microorganisms in natural water may play a significant role in the transformation of As, thereby influencing the toxicity of As in receiving waters. This study clearly suggests that the joint action of As species should be considered in the development of water quality guidelines. To our knowledge this is the first study on the interactive effect of As(III) and As(V) to a cladoceran. Thus, this study suggests that these two species of As, when present together above 0.1 mg l⁻¹ concentration, are toxic to fresh water invertebrates; therefore, pollution with these compounds may adversely affect natural ecosystems.     

Microbial populations in surface films and subsurface waters: Amino acid metabolism and growth

Sea surface microlayer (film) and subsurface microbial populations (biomass and activities) were studied in the Damariscotta (Maine) estuary in May and September, 1987. Dissolved free and combined amino acids (DFAA, DCAA), bacterial numbers, microbial ATP, bacterial and microbial DNA synthesis (via³H-thymidine and³H-adenine), and amino acid (³H-glutamic acid) metabolism were measured. DFAA and DCAA were typically enriched in the surface microlayers relative to surface waters, although utilization of glutamic acid was usually more rapid in subsurface waters, as was incorporation of thymidine. Bacteria represented 12 to 40% of the microbial biomass as determined by ATP, except during microalgal blooms in the microlayer. Bacteria were generally not enriched in the surface films, although ATP usually was enriched. Rain input appeared to deplete population densities but stimulated population activities. Two stations which contained similar microbial populations (as estimated by bacterial counts, chlorophylla and ATP) showed very different microbial activities, apparently due to the effects of a substantial rainstorm on one of the stations. The bacterially-dominated processes utilizing thymidine and glutamic acid were enhanced approx five-fold after the rain. Autotrophic carbon production increased approx two-fold, while total microbal community DNA synthesis (as estimated by adenine incorporation into DNA) increased nearly tenfold. The observations of this study indicate that surface microlayers in the temperate waters off the coast of Maine contain highly active heterotrophic and autotrophic populations. The microbial community responds rapidly to changes in nutrient and dissolved organic matter concentrations resulting from both seasonal and temporal effects, including rain and runoff.     

Manganese in natural waters II. Evidence for microbiological oxidation of Mn (II)

The oxidation of Mn(II) to Mn(IV) in natural waters has been investigated. Various hypotheses have been put forward for the mechanism of oxidation of Mn(II) of which only biological oxidation was found to occur in the aquatic system studied. The effect of adsorption, usually associated with the oxidation of Mn(II) was not observed in our study. The oxidation kinetics can be divided into three periods. The first period is the induction time corresponding to the growth of microorganisms that act as oxidising agents for Mn² _aq ⁺. During this stage Mn² _aq ⁺ remains constant. This period is followed by a decrease in Mn² _aq ⁺ concentration following zero order rate law. Finally in the third period the decrease in Mn² _aq ⁺ follows a first order rate law. The microorganisms acting as oxidising agents for Mn(II) have been identified to be filamentous Gallionella type bacteria and Leptothrix discophora.     

The use of ICP-MS for the analysis of natural waters and an evaluation of sampling techniques

Analytical and sampling methods for a reconnaissance survey of river waters in former metal mining areas of Wales, UK, are considered. A semi-quantitative mode of analysis with a single internal standard, possible by inductively coupled plasma mass spectrometry (ICP-MS) is compared with more conventional quantitative ICP-MS methods using external calibration from aqueous standards. Semi-quantitative analysis can be much quicker than a more rigorous quantitative approach and gives values which agree with fully quantitative data to within 30%, indeed, agreement is often much better than this. A comparison of samples filtered and acidified in the field with untreated samples is also presented. This shows that in most cases it is unnecessary to filter and acidify samples if the storage time before analysis is short (in this case typically less than four days).     

Kinetics of glucose and amino acid uptake by attached and free-living marine bacteria in oligotrophic waters

Kinetics of glucose and amino acid uptake by attached and free-living bacteria were compared in the upper 70 m of the oligotrophic north-western Mediterranean Sea. Potential uptake rates of amino acids were higher than those of glucose in all the samples analysed. Cell-specific potential uptake rates of attached bacteria were up to two orders of magnitude higher than those of total bacteria, both for amino acids and glucose (0.72–153 amol amino acids cell⁻¹ h⁻¹ and 0.05–58.42 amol glucose cell⁻¹ h⁻¹ for attached bacteria and 0.34–1.37 amol amino acids cell⁻¹ h⁻¹ and 0.07–0.22 amol glucose cell⁻¹ h⁻¹ for total bacteria). The apparent K _m values were also higher in attached bacteria than in total bacteria, both for amino acids and glucose. These results would reflect the presence of different uptake systems in attached and free-living bacteria, which is in accordance with the different nutrient characteristics of their microenvironments, ambient water and particles. Attached bacteria show transport systems with low affinity, which characterise a bacterial community adapted to high concentration of substrates. Received: 13 June 2000 / Accepted: 6 December 2000     

Fatty acid profiles of juvenile salmon indicate prey selection strategies in coastal marine waters

Juvenile salmon exhibit high growth rates upon their arrival into the marine environment. Dietary changes from freshwater and estuarine habitats to those derived from the marine environment may play an important role in ultimate adult survival. We measured the total lipid and fatty acid (FA) composition of juvenile Chinook salmon (Oncorhynchus tshawytscha), coho salmon (O. kisutch), and 18 of their potential prey items sampled from coastal waters during their first few months at sea. Coho salmon had significant reductions in their lipid content (% wet weight) between May and June, likely due to early marine growth. We did not find a significant drop between May and June Chinook salmon lipid content, which may indicate an earlier ontogenetic selection to marine prey that are higher in lipids and essential fatty acids (EFAs). Juvenile salmon ate prey of both high and low lipids. Significant FA compositional changes occurred for both coho and Chinook salmon between May and June. In May, the FA profile of juvenile salmon, especially coho salmon, did not resemble their prey items; however, in June, there was a strong correlation between salmon and their common fish prey as determined by gut content analysis. Significant increases in the level of EFAs, especially docosahexaenoic acid (DHA, 22:6n-3) accounted for the majority of the monthly differences in salmon tissue FA composition. In order for juvenile salmon to adequately meet their physiological requirements, they may have adapted to select advantageous prey with higher levels of EFAs, especially DHA, in order to rapidly increase their growth and ultimate survival.     

Catastrophic Reproductive Failure, Terrestrial Survival, and Persistence of the Marbled Salamander

Abstract:  Wide variation in reproductive success is common among amphibians that breed in seasonal ponds, but persistence of adults can buffer against these fluctuations, particularly for long-lived species. We hypothesized that the frequent episodes of catastrophic failure of the marbled salamander ( Ambystoma opacum ) enhance the importance of high terrestrial survival. At Rainbow Bay in South Carolina reproductive success was poor (<1 metamorph/breeding female) in nearly half of the 22 years that the species bred. Complete failure occurred in 6 of 22 years. To study catastrophic failure, we adapted an age-structured, individual-based model with density-dependent growth and survival of larvae. The model was based on extensive data from local field studies and experiments. With consistently good survival in the pond stages, the simulated population required survival probabilities in the upland stages (juveniles and adults) near 0.5/year to persist and near 0.8/year to achieve the increases observed. Catastrophic failure, occurring randomly with probability 0.5/year, created additional fluctuations in the population, raised the thresholds of survival required for persistence, and caused extinction under conditions that were otherwise favorable. The marbled salamander at Rainbow Bay is not at great risk of extinction because of catastrophic failure, but the risk increases dramatically if life span is decreased or frequency of failure is increased. Any reduction in terrestrial survival will have deleterious consequences by reducing the breeding populations at equilibrium, even if it does not jeopardize persistence. Our model provides assessments of risk that can be applied to poorly studied species with similar life histories, such as the endangered flatwoods salamander ( A. cingulatum ).