Determination of arsenic content of some Romanian natural mineral groundwaters

Romania is one of the countries that have natural arsenic groundwater problems. This paper presents the results of a study of arsenic concentration monitoring in natural mineral waters collected from 23 sampling sites located in the northern, central, and western regions of Romania. The sampling sites are both natural springs and drilled wells. The graphite furnace atomic absorption spectrometry was used for arsenic content determination. The Piper??s classification principle was applied in order to find out the hydrochemical type of the analyzed waters. Depending on the concentration of arsenic, the water analyzed can be classified into three main categories: (1) mineral natural waters containing less than 10???g/L arsenic, (2) mineral natural waters containing arsenic at concentrations several times higher than the limit of 10???g/L but less than 100???g/L, and (3) mineral natural waters containing arsenic at concentrations of ten to a hundred times higher than the allowed limit of 10???g/L. The last-mentioned waters are of bicarbonatate sodium type and were sampled from seven sources only, being prohibited for human and animal use.     

水体中酚类化合物分光光度分析方法的研究

对国内外水体中酚类化合物现有的分光光度分析方法进行了文献综述 ,内容包括可见光分光光度法、紫外光分光光度法、荧光分光光度法和流动注射分光光度法。在总结归纳的基础上 ,提出了水体中酚类化合物分光光度分析方法的发展方向。     

Determination of trace transition metals in environmental matrices by chelation ion chromatography

Trace transition metals (Fe^3?+?, Mn, Cu, Cd, Co, Zn, Ni) in environmental samples were analyzed by chelation ion chromatography using a mixed bed ion-exchange column with pyridine-2,6-dicarboxylic acid (PDCA) and oxalic acid as eluent and large volume direct injection (1,000 ??l). The two eluents, PDCA and oxalic acid, were tested, and repeatability and detection limits were compared. The total analysis time was ~15 min. The separation with PDCA was more successful than that obtained with acid oxalic. It was observed that utilizing PDCA resulted in lower detection limits, higher repeatability, and a quantitative detection of Cd and Mn, which coelute as a single peak when using the oxalic acid. At last, the PDCA calibration graphs resulted linear (r ²?>?0.999) in the range 0.4?C1,000 ??g/L. The procedure was applied to the analysis of metals in soils and in water samples. The results obtained from the analysis of natural waters have demonstrated that the method is simple and efficient, therefore, can be used for the determination of metals in natural waters using a continuous and automatic monitoring system.     

Sampling and analyses of colloids at the Drigg low level radioactive waste disposal site

Water samples have been extracted from inside (from standpipes) and from outside (from boreholes) of the trenches at the low level radioactive waste disposal site at Drigg in Cumbria, UK. The samples were taken anaerobically from between 8.5 and 10.0 m below the surface using a submersible pump at low flow rates to ensure that the waters in the standpipes and boreholes were maintained at constant levels. To ensure representative samples, the Eh, pH. conductivity, temperature, iron and dissolved oxygen concentrations of the waters were taken during initial purging and during sampling. The gross tritium, gross non-tritium beta, gross alpha and gamma activities of each sample were determined using suitable sample preparation and counting techniques. Samples were then anaerobically, sequentially filtered through 12 microm, 1 microm, 30 kDa and 500 Da filter membranes. The filtrates were analysed for gross alpha, gross non-tritium beta and gamma activities. SEM and STEM analyses were used to determine the colloid population. An energy dispersive analyser on the SEM was used to determine the major elements present in the colloids. UV-visible spectrophotometry, fluorescence spectrophotometry and high performance size exclusion liquid chromatography were used to analyse the waters before and after treatment with ion exchange materials to determine whether natural organic matter was present in the waters. Results showed that two major types of colloids (iron containing colloids and silicon containing colloids) were present in the waters. There were also a small number of other colloids that contain, as major elements, aluminium, calcium and chromium. Organic colloids were also present. The majority of the radioactivity in the waters was due to tritium. Waters taken from outside the trenches contained low levels of non-tritium beta activities and alpha activities which were lower than the minimum detectable amount. Waters taken from the trenches contained non-tritium beta activities and low levels of alpha emitters. Filtration of the trench waters showed that some of the alpha activity was retained by the 30 kDa and 500 Da membranes suggesting that this activity was associated with small colloids. Radioactivity was not found to be associated with colloids present in the waters taken from outside the trenches. Possible reasons for this observation could be that radionuclide bearing colloids have not yet reached the far-field or that the radionuclide concentration is diluted to below the minimum detectable amount. After concentrating two of the samples by factors of x20 and x 16 respectively, 2.4+/-0.1 and 0.6+/-0.1 Bq dm(-3) of 137Cs were measured.     

Evaluation of Storage and Filtration Protocols for Alpine/Subalpine Lake Water Quality Samples

Many government agencies and other organizations sample natural alpine and subalpine surface waters using varying protocols for sample storage and filtration. Simplification of protocols would be beneficial if it could be shown that sample quality is unaffected. In this study, samples collected from low ionic strength waters in alpine and subalpine lake inlets and outlets in the western United States were used to evaluate (1) effects of refrigerated storage time on the chemistry of unfiltered samples, and (2) differences in sample filtration protocols. No analytes exhibited significant changes when stored less than 48 h. Six analytes (pH, sodium, ammonium, potassium, chloride, sulfate) exhibited statistically significant (but small) changes when storage time exceeded 48 h. Two analytes (calcium, nitrate) were significantly higher when samples were field filtered than when filtered in the laboratory, but the differences were also small. For waters similar to those in this test, unfiltered refrigerated samples may be stored up to 48 h without compromising sample quality. The small differences between field and lab filtration do not justify the expense, training, and contamination risk of field filtration.     

Assessment of toxic heavy metals in urban lake sediments as related to urban stressor and bioavailability

Aquatic pollution pose a serious challenge to the scientific community worldwide, since lakes or reservoirs find multifarious use and most often their water is used for drinking, bathing, irrigation, and aquaculture. Nine metals and several physicochemical parameters, from four sampling sites in a tropical lake receiving the discharges from a thermal power plant, a coal mine, and a chlor-alkali industry, were studied from 2004 to 2005. Pertaining to metal pollution, the site most polluted with heavy metals was Belwadah, i.e., waters and sediments had the highest concentration of all the metals examined. The reference site was characterized by the presence of low concentrations of metals in waters and sediments. Following the water quality monitoring, 2-month field phytoremediation experiments were conducted using large enclosures at the discharge point of different polluted sites of the lake. During field phytoremediation experiments using aquatic macrophytes, marked percentage reduction in metals concentrations were recorded. The percentage decrease for different metals was in the range of 25% to 67.90% at Belwadah (with Eichhornia crassipes and Lemna minor), 25% to 77.14% at Dongia nala (with E. crassipes, L. minor and Azolla pinnata), and 25% to 71.42% at Ash pond site of G.B. Pant Sagar (with L. minor and A. pinnata). Preliminary studies of polluted sites are useful for improved microcosm design and for the systematic extrapolation of information from experimental ecosystems to natural ecosystems.     

Testing the MAGIC acid rain model in highly organic,low-conductivity waters using multiple calibrations

Accurate predictions of acid precipitation effects on water resources are important in order to allow a better understanding of various pollution control strategy outcomes. Dynamic geochemical models have been developed to address this need, but have to be tested under a variety of environmental conditions to provide confidence in their predictions. The most commonly used aquatic acidification model in North America and Europe is the model of acidification of groundwater in catchments (MAGIC). Though extensively used, MAGIC has never been tested in catchments with extremely low ionic strength water and high in natural organic acids (NOAs) from wetlands, two conditions which are common in large parts of Canada. We calibrated the model for two catchments located in Nova Scotia, Canada, which had some of the most dilute freshwaters reported in the literature and very high NOA. We also evaluated the variability inherent in calibration data sets by using five separate data sets collected over a 15-year period at the same sites. We show good model simulations for the main cations and anions in catchment waters. However, modeling pH is more difficult in the highly organic waters and requires modification to the acid dissociation constants. Calculated acid neutralization capacity can also be more difficult to model due to the low ion content making small errors more important. In theory, multiple calibrations of a model at a same site should produce identical hindcasts and predictions. In reality, the multiple calibrations produced a series of similar, but not identical outcomes which give a probable range of past values and future outcomes. We feel that this practical approach to validation is a useful addition to the arsenal of model testing tools.     

Assessment Of A Natural Wetland For Use In Wastewater Remediation

An environmental study was conducted to assess various aspects of the water and sediment quality of a natural wetland to determine its feasibility for advanced wastewater treatment in Louisiana. Nitrate (NO₃), nitrite (NO₂), ammonia (NH₄), total Kjeldahl nitrogen (TKN), total phosphorus, chloride, total organic carbon, pH, trace metals, fecal coliform, dissolved oxygen (DO), and biochemical oxygen demand (BOD) were monitored. Productivity of a dominant shrub, Iva frutescens, in the wetland was also assessed. Research results indicated that gradients of chloride and salinity concentrations showed a broad mixing of the discharged fresh water into the more saline natural brackish waters. This provided an ideal pattern for nutrient assimilation by the receiving marsh. NH₄ was reduced in the range of 50–100% when all combinations of sources and outflows were considered. For total phosphorus and TKN, reduction ranged from 0–95.1% and 11.2–89.7%, respectively. Some nutrient concentrations in the effluent outlet, NO₃ in particular, were lower than background concentrations found in the reference wetland. Sediment and water showed no significant deficiency or toxicity problems for the major nutrients and metals analyzed. The secondary effluent discharges had little demonstrable negative impact on the wetland during the study period from 1995 to 1996.     

Emergy-based evaluation of system sustainability and ecosystem value of a large-scale constructed wetland in North China

Constructed wetland has been widely adopted to deal with degraded natural wetlands and water bodies; thus, more attention should be focused on ecological–economic sustainability and ecological efficiency of these projects for long-term success. Emergy accounting was conducted to investigate the energy and resource flows in constructed wetlands during the restoration process. Emergy-based indexes were adopted to evaluate the sustainability of a pilot large-scale constructed wetland in a large wetland restoration project in North China, carried out to enhance the river water quality and offset the degradation of natural wetland. Emergy and emdollar values for ecosystem services and natural capital were also calculated. The results showed that when outflow was considered as the product, the studied large-scale constructed wetland was more self-supporting and could be operated with lesser financial investment, although the waste treatment efficiency and the sustainability index were lower than conventional small-scale treatment constructed wetlands. Compared with natural wetlands, more visits from tourists and lesser financial investment coming in as feedback into the wetland would reduce system environment loading and promote system self-support ability, ultimately generating sustainability. In addition, the studied large-scale constructed wetland can effectively simulate energy and resource flows of natural wetland ecosystem and contribute a roughly equal value of ecosystem services in term of gross primary production. The studied large-scale constructed wetland can successfully achieve ecosystem functions as replacement for natural wetland and hasten the restoration process, although the restoration effectiveness of ecosystem structures in terms of living biomass and water using emergy-value accounting is still inconclusive.     

Snapshot of Vibrio parahaemolyticus densities in open and closed shellfish beds in Coastal South Carolina and Mississippi

Vibrio parahaemolyticus is a Gram negative, halophilic bacterium that is ubiquitous in warm, tropical waters throughout the world. It is a major cause of seafood-associated gastroenteritis and is generally associated with consumption of raw or undercooked seafood, especially oysters. This study presents a snapshot of total V. parahaemolyticus densities in surface waters and shellstock American oysters (Crassostrea virginica) from open and closed shellfish harvesting areas, as well as “more rural areas” on two different US coasts, the Atlantic and the Gulf. Sampling was conducted from 2001 to 2003 at five sites near Charleston/Georgetown, SC and at four locations in the Gulfport/Pascagoula, MS area. V. parahaemolyticus numbers were determined by a direct plating method using an alkaline-phosphatase-labeled DNA probe targeting the species-specific thermolabile hemolysin gene (tlh) that was used for identification of bacterial isolates. The greatest difference between the two coasts was salinity; mean salinity in SC surface waters was 32.9 ppt, whereas the mean salinity in MS waters was 19.2 ppt, indicating more freshwater input into MS shellfish harvesting areas during the study period. The mean V. parahaemolyticus numbers in oysters were almost identical between the two states (567.4 vs. 560.1 CFU/g). Bacterial numbers in the majority of surface water samples from both states were at or below the limit of detection (LOD?=?<10 CFU/mL). The bacterial concentrations determined during this study predict a low public health risk from consumption of oysters in shellfish growing areas on either the Gulf or the Atlantic US coast.     

Spatial distribution and risk assessment of heavy metals in sediments from a hypertrophic plateau lake Dianchi, China

The sediment in Dianchi Lake, a hypereutrophic plateau lake in southwest China, was investigated and the concentration of heavy metals (Cu, Cr, Ni, Zn, Pb, Fe, Mn, and Cd) in the sediment and sediment properties were determined. Their spatial distribution and sources were analyzed using multivariate statistics. The result indicated that the studied metals exhibited three distinct spatial patterns; that is, Cu, Pb, Zn, and Ni had a similar distribution, with a concentration gradient from the north to the south part of the lake; Cd and Cr presented a similar distribution; Fe and Mn presented a quite different distribution than other metals, which indicated their different sources and geochemistry processes. Correlation and cluster analysis (CA) provided origin information on these metals and the CA result was observed corresponding to those three spatial patterns. Principal component analysis further displayed metal source and driving factors; that is, Cu, Pb, Zn, Ni, Cd, and Cr were mainly derived from anthropogenic sources, and Fe and Mn were mainly the result of natural processes. Sediment assessment was conducted using geoaccumulation index (Igeo), potential ecological risk indices, and USEPA guidelines. The result indicated that, generally, Cd was the most serious risk metal; Pb and Cu posed moderate potential ecological risk; Cr, Zn, and Ni had slight ecological risk; Fe and Mn had little risk. Comparison of the assessment tools showed that each of the methods had its limitation and could bias the result, and the combined use of the methodologies and local knowledge on lithology or metal background value of soil in the practice would give a more comprehensive understanding of the metal risk or pollution. Statistical analysis also indicated that nutrients had different impacts on Fe, Mn, and trace elements, which implied that in the assessment of metal risk, nutrients impact should be taken into consideration especially for eutrophic waters.     

Field evaluation of an innovative stormwater treatment device—the StormvaultTM system

This paper reports the results obtained for the determination of Ba concentrations in mineral groundwater samples collected from drilled outlets located in the counties of Covasna and Harghita (34 sampling points), in five expeditions (spring, summer, and autumn), during 3 years: 2005, 2006, and 2007. The experimental data show that there are some sampling sites in which the barium concentration exceeds 1 mg/L, which is the maximum concentration admitted for barium. These mineral natural waters could be used only for therapeutic purposes. All other analyzed natural mineral waters are proper as both drinking and therapeutic water. By means of a principal component analysis a statistical approach was performed, using the data obtained during those analyzing processes. The distribution of the water saturation indexes with respect to a series of mineral species (alstonite, barite, barytocalcite, nitrobarite, sanbornite, and witherite) suggests that barium tends to remain in solution as ionic species in different concentrations and to be further carried away as such.     

Cyanotoxin management and human health risk mitigation in recreational waters

The occurrence and severity of harmful cyanobacterial or blue-green algal blooms (HABs) have increased in recent decades, posing a serious threat of illness to humans. In some countries, water contaminated with cyanotoxins that is used for drinking or haemodialysis has posed a particularly serious risk. However, it is now recognized that recreational exposure to natural toxins by skin contact, accidental swallowing of water or inhalation can also cause a wide range of acute or chronic illnesses. In this review, we focus on the importance of cyanotoxin management in recreational waters. The symptoms related with HAB poisonings, the recommended safety concentrations limit for cyanobacteria and cyanotoxins in such waters, as well as early health hazard indicators of their presence and their monitoring are all discussed. We also present in this review an overview of the methods developed in recent decades for eliminating cyanobacteria and the toxic compounds that they produce.     

Variation of total organic carbon content along the stream Harsit, Eastern Black Sea Basin, Turkey

The TOC in surface waters and wastewater is an important analytical parameter describing the total content of all organic substances containing carbon. In practice, the TOC originated from natural and anthropogenic sources, and even if it is not directly responsible for dangers on human health, its determination is important for any kind of water that is used by public. The aim of this study was to determine variation of total organic carbon (TOC) and total carbon (TC) content in the stream Harsit, which courses in Eastern Black Sea Region, Turkey. Sampling was fortnightly conducted in each of the four seasons between March 2009 and February 2010. A total of 230 water samples were collected from ten sampling stations along the main branch of the stream Harsit with 143 km of length. Obtained TOC values were evaluated and used to classify the water quality of stream Harsit, according to the Turkish Water Pollution Control Regulation (TWPCR). The annual average TOC content values for the stations were found between 2.33 and 6.97 mg/L. It was seen that the TOC content have increased along the streamcourse of Harsit until the fourth station, where reaches its maximum value. The TOC content, then, has decreased and the minimum value was observed in the eighth station. The results showed that, except in winter season, maximum TOC content observed in many of the water samples were above Class I water standard indicated in TWPCR, which classifies the water resources according to the different area of uses. It was also found that TOC has a small contribution to TC and the highest TOC content in stream waters were measured in Gumushane station where direct discharge of city wastewaters and solid waste dumping to the stream were observed.     

Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.     

Quantifying health risk reductions from implementation of a passive net alkaline wetland

The potential effectiveness of a constructed passive net alkaline wetland in reducing human health risks from heavy metals in surface waters was evaluated by using a multimedia model. Scenarios were developed using information available from site reports, state, federal, and standard engineering sources. The scenarios replicated observed heavy metal concentrations in the waters of a volunteer wetland and estimated the concentrations after implementation of a constructed passive net alkaline wetland. The greatest reductions in risks are expected to occur soon after construction, with children benefiting more than adults.     

Field cryofocussing hydride generation applied to the simultaneous multi-elemental determination of alkyl-metal(loid) species in natural waters using ICP-MS detection

Two hydride generation manifold systems, utilizing flow injection and cryotrapping techniques for alkyl-metal(loid) speciation analysis in natural waters, are described in this paper. They provide shipboard capacity for simultaneous derivatization of analytes with NaBH4 and cryotrapping of the generated products in a field packed column at -196 degrees C. The first system is a large-volume hydride generator, using a reagent-injection flow technique as a flow batch type, that has been fully optimized and applied to the simultaneous detection of alkylated species in estuarine waters. The technique permits the analysis of a large volume sample (0.5-11) at a sampling rate of 3 h-1. The second is an online continuous flow hydride generator. A sampling rate of 3-12 h-1 can be achieved with samples of 0.1-0.51. In addition, shipboard operation eliminates major problems related to sample pretreatment, transport and storage. Ultra-trace multi-element determination is finally performed in the laboratory by cryogenic GC hyphenated with ICP-MS. Routine detection limits of 0.5-10 pg (as metal) for 0.51 water samples were achieved for the selected alkyl-metal(loid) species of arsenic, germanium, mercury and tin. Concentrations of various species, obtained from water samples taken from the Rhine estuary, are also presented. These species include alkylated arsenic compounds, other than methyl derivatives, that have been tentatively identified and are reported here for the first time.     

流动注射氯化亚锡还原光度法测定水中总磷

建立了流动注射氯化亚锡还原光度法测定水中总磷的方法.改进了氯化亚锡的配制方法,优化了试验条件,方法检出限为0.02 mg/L,精密度与准确度均符合要求.应用该方法测定天然水样,分析速度加快,结果令人满意.     

The sensitive and selective determination of aluminium by spectrofluorimetric detection after complexation with N-o-vanillidine-2-amino-p-cresol

A simple, easy to use and selective spectrofluorimetric method for the determination of trace levels of aluminium has been developed. A new Schiff base, N-o-vanillidine-2-amino-p-cresol (OVAC), has been synthesized and its fluorescence activity with aluminium investigated. Based on this chelation reaction, a spectrofluorimetric method has been developed for the determination of aluminium in samples buffered at pH 4.0 using acetic acid-sodium acetate. The chelation reaction between Al(iii) and N-o-vanillidine-2-amino-p-cresol was very fast, requiring only 20 min at room temperature to complex completely. The excitation and emission wavelengths were 423.0 and 553.0 nm, respectively, at which the OVAC-Al complex gave the maximum fluorescence intensity at pH 4.0 in a 50% ethanol-50% water medium. The interference from fluoride ions was minimized by the addition of Be(2+). Other ions were found not to interfere at the concentrations likely to be found in natural waters. Under these conditions, the calibration plot was linear up to 1000 microg L(-1) (r = 0.999). The limit of detection (3sigma) for the determination of Al(iii) was 0.19 microg L(-1) and the precision for multiple determinations of 3 ng mL(-1) Al(iii) prepared in ultra-pure water was found to be 0.29% (n = 16). The Schiff base ligand could be used to determine ultra-trace aluminium from natural waters. Analysis of environmental certified reference materials showed good agreement with the certified values. The procedure was found to be equally applicable to both fresh water and saline solutions (including sea water) using either normal external calibration or the standard additions method.     

How best to quantify soil seed banks in arid rangelands of the Nama Karoo?

Sampling design and three sample treatments prior the application of the seedling emergence method were tested in order to find the best method for seed bank quantification in arid Nama Karoo rangelands. I analyzed species composition and seed densities by contrasting undercanopy and open-matrix samples from two soil depths and by comparing the effects of cold-, heat-, and no stratification on germination rates of species in a greenhouse setting. The soil seed bank showed minimal similarity to the standing vegetation, with only 20 plant species germinated. Spatial distribution of seeds was highly heterogeneous. Nearly 90% of germinated seeds were located in 0- to 4-cm compared to >4- to 8-cm soil depth. Undercanopy seed banks contained significantly more species and seeds than open-matrix seed banks. Neither the number nor the diversity of seeds germinated differed significantly among the three treatments. Cold stratification tended to detect more species and seeds only at >4- to 8-cm soil depth. The results highlight the importance of spatial heterogeneity in the accurate evaluation of soil seed banks in the arid Nama Karoo and the importance of considering seasonal variability in the availability of readily germinable seeds. Data also suggest that sample pretreatment in germination trials may give little return for cost and effort, which emphasizes that it is more important to choose the sampling design most likely to give a representative number of seed bank species. Further studies are needed to analyze seed bank dynamics and species-specific germination requirements to promote recruitment of plant taxa underrepresented in the seed bank.