Estuarine mixing behavior of colloidal organic carbon and colloidal mercury in Galveston Bay, Texas

Mercury (Hg) in estuarine water is distributed among different physical phases (i.e. particulate, colloidal, and truly dissolved). This phase speciation influences the fate and cycling of Hg in estuarine systems. However, limited information exists on the estuarine distribution of colloidal phase Hg, mainly due to the technical difficulties involved in measuring it. In the present study, we determined Hg and organic carbon levels from unfiltered, filtered (<0.45 μm), colloidal (10 kDa-0.45 μm), and truly dissolved (<10 kDa) fractions of Galveston Bay surface water in order to understand the estuarine mixing behavior of Hg species as well as interactions of Hg with colloidal organic matter. For the riverine end-member, the colloidal fraction comprised 43 ± 11% of the total dissolved Hg pool and decreased to 17 ± 8% in brackish water. In the estuarine mixing zone, dissolved Hg and colloidal organic carbon showed non-conservative removal behavior, particularly in the low salinity (<15 ppt) region. This removal may be caused by salt-induced coagulation of colloidal matter and consequent removal of dissolved Hg. The particle-water interaction, K(d) ([particulate Hg (mol kg(-1))]/[dissolved Hg (mol L(-1))]) of Hg decreased as particle concentration increased, while the particle-water partition coefficient based on colloidal Hg and the truly dissolved Hg fraction, K(c) ([colloidal Hg (mol kg(-1))]/[truly dissolved Hg (mol L(-1))]) of Hg remained constant as particle concentration increased. This suggests that the particle concentration effect is associated with the amount of colloidal Hg, increasing in proportion to the amount of suspended particulate matter. This work demonstrates that, colloidal organic matter plays an important role in the transport, particle-water partitioning, and removal of dissolved Hg in estuarine waters.     

Changes in the sorption and rate of 17β-estradiol biodegradation by dissolved organic matter collected from different water sources

The potential biodegradation and subsequent transformation of 17β-estradiol (E2) to estrone (E1) were examined in the presence of various dissolved organic matter (DOM) isolated from effluent, river and lake waters. In addition, estrogenicity was estimated in association with the removal of E2 via its sorption onto DOM and biodegradation. The more biodegradable lake-derived DOM promoted more extensive transformation of E2 into E1 than the effluent organic matter through a biodegradation process. Overall, under all conditions, biodegradation dominated the removal of E2 in water. The increased dissolved organic carbon (DOC) concentrations in river and lake-derived DOM (e.g. 6.5 mg C L(-1)) reduced the removal of E2 by decreasing its biodegradation due to the moderate sorption of E2 onto DOM. The effluent organic matter showed greater removal of E2 via biodegradation, as well as significantly high sorption. This was associated with a large amount of hydrophobic fulvic acid (FA)- and humic acid (HA)-like organic components, as shown by the small increase in the specific UV absorbance at 254 nm (SUVA(254)). An increase in the DOC concentration reduced the removal of E2, resulting in high estrogenicity. The present study suggests that both organic composition and DOC concentration influenced the removal of E2 and, therefore, should be fully considered when assessing estrogenicity and its impacts on the aquatic environment.     

Monitoring requirements for groundwaters under the influence of reclaimed water

Monitoring groundwaters under the influence of reclaimedwater must consider the major constituents of concern inreclaimed water. This research focused on the fate ofdissolved organic carbon and nitrogen species at field siteslocated throughout the Southwestern United States. Awatershed approach was developed to predict the fate ofdissolved organic carbon as a function of the drinking waterdissolved organic carbon concentration and the totaldissolved solids concentration in the reclaimed water. Extensive characterization of the dissolved organic carbonrecovered from groundwaters under the influence of reclaimedwater was done. With the exception of fluorescencespectroscopy, the dissolved organic carbon present ineffluent organic matter was similar in structure, characterand reactivity as compared to natural organic matter. Evidence for sustainable nitrogen removal mechanisms duringgroundwater recharge with reclaimed water was obtained. Theautotrophic reaction between ammonia and nitrate appears to amechanism for the removal nitrogen in a carbon-depletedenvironment. The monitoring tools and methodologiesdeveloped in this research can be used to assure protectionof public health and determine the sustainability of indirectpotable reuse projects.     

A brief overview of modern directions in marine DOC studies part II--recent progress in marine DOC studies

Progress made in analytical techniques allows the formulation of new concepts in the biogeochemistry of organic carbon. The second part of our review summarizes the latest evolution and introduces new ideas in the biogeochemistry of marine dissolved organic carbon (DOC). Via classification of different fractions and sources of DOC, characterization of its composition, age and availability for bacterial utilization, and fate of DOC, we show the role of DOC in the global carbon cycle and the significance of bulk DOC in the oceans. Special emphasis is placed on the microbial loop in the cycling of DOC and its relation with higher trophic levels (phytoplankton and zooplankton). Significant progress has also been made in the study of the roles of colloidal organic material in metal complexation, ultraviolet radiation in dissolved organic matter photochemical oxidation, and chromophore-containing constituents of DOC as the signature of DOC for satellite observations. The importance of bulk DOC in the global carbon cycle requires the inclusion of this fraction in the regional and global carbon models. We predict that future DOC study in the ocean will focus on the development of sophisticated, almost continuously recording, moored DOC instrument arrays for the monitoring of small-scale DOC horizontal and vertical patchiness; widespread time series stations including estuarine, coastal and open environments; more detailed chemical characterization of different fractions of organic carbon from diverse marine habitats; parameterization of predictive models of DOC cycling on regional and global scales, incorporating the microbial loop; and finally, monitoring of DOC dynamics from satellites on regional and global scales.     

Assessment of relative accuracy in the determination of organic matter concentrations in aquatic systems

Accurate determinations of total (TOC), dissolved (DOC) and particulate (POC) organic carbon concentrations are critical for understanding the geochemical, environmental, and ecological roles of aquatic organic matter. Of particular significance for the drinking water industry, TOC measurements are the basis for compliance with US EPA regulations. The results of an interlaboratory comparison designed to identify problems associated with the determination of organic matter concentrations in drinking water supplies are presented. The study involved 31 laboratories and a variety of commercially available analytical instruments. All participating laboratories performed well on samples of potassium hydrogen phthalate (KHP), a compound commonly used as a standard in carbon analysis. However, problems associated with the oxidation of difficult to oxidize compounds, such as dodecylbenzene sulfonic acid and caffeine, were noted. Humic substances posed fewer problems for analysts. Particulate organic matter (POM) in the form of polystyrene beads, freeze-dried bacteria and pulverized leaf material were the most difficult for all analysts, with a wide range of performances reported. The POM results indicate that the methods surveyed in this study are inappropriate for the accurate determination of POC and TOC concentration. Finally, several analysts had difficulty in efficiently separating inorganic carbon from KHP solutions, thereby biasing DOC results.     

Distribution and speciation of selected metals in surface sediments, from the tropical Zuari estuary, central west coast of India

Estuarine sediments are major reservoirs for the metals. Distribution and mobility of metals within estuaries depends strongly on their specific chemical form. In the present study, surface sediments from Zuari estuary, Goa were analysed by a sequential procedure for Fe, Mn, Cu, Zn, Cr and Co to determine their distribution in five geochemical phases (Exchangeable, carbonate, Fe-Mn oxide (reducible) organic bound (oxidisable) and residual). The total metal content, sand, silt, clay and organic carbon were also determined of the surface sediments. The total metal contents were found to be greater than the background concentrations of average shale values as well as to that of earlier studies indicating enrichment probably due to the anthropogenic origin of metals. The results obtained from sequential procedure showed that among the studied elements, Mn and Co are potentially available in the bioavailable fractions (exchangeable, carbonate and Fe-Mn oxide bound fractions) indicating their importance in toxicity whereas rest of the metals viz. Fe, Cu, Zn and to some extent Cr are largely available in residual phase although they are available in other fractions. The main source of metals to the estuary is mining and its associated activities in the study area. Chemical speciation by sequential extraction procedure has helped in assessing the mobility, bioavailability, diagenesis and toxicity of metals and hence giving a better insight into the ultimate fate of pollutants, which are introduced into the estuarine environment. To understand the risk of the metals to the sediment dwelling organisms the data were compared with the Sediment Quality Values (SQV) using SQUIRT. Also, correlation and Factor analysis were carried out to understand the associations of metals in the different fractions with sand, silt, clay, organic carbon and with other metals.     

Assessing the removal potential of soil-aquifer treatment system (soil column) for endotoxin

Soil-aquifer treatment (SAT) of wastewater is an increasingly valued practice for replenishing aquifers due to ease of operation and low maintenance needs and therefore low cost. In this study, we investigated the fate of endotoxins through laboratory-scale SAT soil columns over a four month period. The effluent of rapid sand filtration was run through the columns under gravity flow conditions. Four SAT columns were packed with four different filter materials (fine sand, medium sand, coarse sand and very coarse sand). The effluent of rapid sand filtration (average dissolved organic carbon (DOC) = 4 mg l(-1) and average endotoxin concentration = 4 EU ml(-1)) was collected from a domestic wastewater treatment plant in Sapporo, Japan. DOC removal ranged from 12.5% to greater than 22.5% during the study, with DOC levels averaging 3.1 and 3.5 mg l(-1) for the SAT columns packed with different soils. Endotoxin transformation exhibited different profiles, depending on the time and soil type. Reduction in endotoxin concentration averaged 64.3% and was as high as 86.7% across the soil columns 1, 2, 3 and 4, respectively. While DOC removal was gradual, the reductions in endotoxin levels were rather rapid and most of the removal was achieved in the top layers. Soil with a larger grain size had lower efficiency in removing endotoxin. Tests were performed to evaluate the transformation of organic matter showing endotoxicity and to determine the mechanisms responsible for changes in the structural and size properties of dissolved organic matter (OM) during SAT. Dissolved OM was fractionated using Sep-Pack C18 Cartridges into hydrophobic and hydrophilic fractions. Dialysis tubes with different molecular weight cut-offs were used to perform size fractions of OM showing endotoxicity. Evaluation of the transformation of organic matter showing endotoxicity during SAT indicated that both hydrophobic and large molecules were reduced. Moreover, experimental findings showed that adsorption test data fit to the Freundlich isotherm and were affected by the particle grain size with higher adsorption capacity for fine and medium sand.     

Evaluating the Efficiency of Coagulation in the Removal of Dissolved Organic Carbon from Reservoir Water using Fluorescence and Ultraviolet Photometry

The present study used ultraviolet absorption (UVa) and the florescence intensity (FI) to evaluate the coagulation efficiency for removing dissolved organic carbon (DOC) in the raw water from Min-Ter, Li-Yu-Ten and Yun-Ho-Shen reservoirs in Taiwan. The results indicated that the ratio of DOC removal rate and FI removal rate was maintained at about 1 at various coagulant dosages. However, the ratio of DOC removal rate and UVa removal rate decreased as the coagulant dosage increased. In addition, after coagulation, the use of florescence intensity instead of total organic carbon (TOC) is better than UVa for measuring the DOC removal rate of the raw waters gathered in different months from the three reservoirs. Furthermore, a good linear relationship between florescence intensity and DOC removal rate was observed, and the DOC/FI ratio of raw water from each reservoir can be used to predict the DOC residual concentration after enhanced coagulation. This result shows that fluorescence analysis can be used for on-line and continuous monitoring the effectiveness of organic matter removal in water treatment.     

Soil Aquifer Treatment (SAT) as a Natural and Sustainable Wastewater Reclamation/Reuse Technology: Fate of Wastewater Effluent Organic Matter (EfOM) and Trace Organic Compounds

Through the use of innovative analytical tools, the removal/transformation of wastewater effluent organic matter (EfOM) have been tracked through soil aquifer treatment (SAT). While the total amount of EfOM is significantly reduced by SAT, there are trends of shorter term versus longer term removals of specific EfOM fractions. The preferential removal of non-humic components (e.g., proteins, polysaccharides) of EfOM occurs over shorter travel times/distances while humic components (i.e., humic substances) are removed over longer travel times/distances, with the removal of both by sustainable biodegradation. Dissolved organic nitrogen (DON), a surrogate for protein-like EfOM, is also effectively removed over shorter term SAT. There is some background humic-like natural organic matter (NOM), associated with the drinking water source within the watershed, that persists through SAT. While most effluent-derived trace organic compounds are removed to varying degrees as a function of travel time and redox conditions, a few persist even through longer term SAT.     

Heavy metal concentrations in water and sediments in Tasik Chini, a freshwater lake, Malaysia

The purpose of this paper are to determine the concentration of heavy metals namely cadmium (Cd), copper (Cu) and lead (Pb) in water and sediment; and to investigate the effect of sediment pH and sediment organic matter on concentration of cadmium, copper and lead in sediment at oxidation fraction. For this purpose the concentration of heavy metals were measured in water and sediments at 15 sites from Tasik Chini, Peninsular Malaysia. The sequential extraction procedure used in this study was based on defined fractions: exchangeable, acid reduction, oxidation, and residual. The concentration of heavy metals in residual fraction was higher than the other fractions. Among the non-residual fractions, the concentration of heavy metals in organic matter fraction was much higher than other fractions collected from all sampling sites. The pH of the sediment in all sites was acidic. The mean pH ranges from 4.8 to 5.5 with the higher value observed at site 15. Results of organic matter analysis showed that the percentage of organic matter present in sediment samples varies throughout the lake and all sites of sediments were relatively rich in organic matter ranging from 13.0% to 34.2%. The highest mean percentage of organic matter was measured at sampling site 15, with value of 31.78%.     

Study of the effect of pH, salinity and DOC on fluorescence of synthetic mixtures of freshwater and marine salts

In order to provide support for the discussion of the fate of organic matter in estuaries, a laboratory simulation was performed by changing freshwater ionic strength, pH and organic matter content. The change in spectroscopic characteristics caused by variations in salinity, pH and organic matter concentration in the filtered samples was observed by UV-Vis and fluorescence spectroscopy. The increase in emission fluorescence intensity of dissolved organic matter (DOM) due to increasing salinity (in the range 0 to 5 g l-1) is affected by the pH of the samples. The emission fluorescence intensity at the three maxima observed in the fluorescence spectra, is linearly correlated with dissolved organic carbon (DOC) concentration at several salinity values in the same sample. The increase in organic matter concentration caused a shift in the emission peak wavelength at 410 nm for several salinity values. We concluded that it is necessary to take into account the influence of salinity and pH on emission fluorescence of dissolved organic matter if it is to be used as a tracer in estuarine or near shore areas.     

气相色谱-质谱法分析污水中溶解态有机物

采用0.45μm玻璃纤维滤膜将污水分离为悬浮态和溶解态有机物质,以二氯甲烷为萃取剂,采用液液萃取-气质联用法对污水中溶解态有机物进行测定,同时还对萃取条件(萃取次数,萃取时间,无机盐加入量)进行优化.结果表明:萃取回收率最高的是每个pH范围各萃取2次、静置5 min,氯化钠加入15g.该方法分析时间短,准确度好(样品平均加标回收率为91.1％ ～ 103％),精密度高(相对标准偏差小于5％),易于操作.     

燃烧氧化-非分散红外吸收测定水中总有机碳方法的改进

总有机碳测定的方法分为差减法和直接法。现对测定方法进行改进,将差减法和直接法测定结果结合,先将样品进行酸化初步吹扫,再使用差减法测定总有机碳。试验结果显示,无论在标准曲线、精密度试验、加标回收试验还是标准样品测定方面,改进法均优于直接法测定结果,且能较好地缩短测量时间。     

Profiling and monitoring of DOM in brewery wastewater and treated wastewater

Dissolved organic matter (DOM) in raw and treated wastewater from two breweries in Thailand was profiled and monitored for the purpose of water reclamation. The wastewater and the effluent from the use of an upflow anaerobic sludge blanket (UASB) and activated sludge (AS) were collected and analyzed through a resin fractionation method using the fluorescent excitation?Cemission matrix (FEEM) technique. The results revealed that the major organic fractions in the brewery wastewater were hydrophobic acid (HPOA) and hydrophilic base (HPIB), accounting for 65% of total dissolved organic carbon (DOC) mass for brewery A and 56% of total DOC mass for brewery B. The FEEM results indicated that the organic matter in the wastewaters of both breweries were mainly composed of tryptophan-like substances, represented by peaks C (230 nm_Ex/340?C365 nm_Em) and D (265?C295 nm_Ex/315?C390 nm_Em), and humic-like substances, represented by peaks E (290 nm_Ex/400 nm_Em), F (330?C335 nm_Ex/395?C410 nm_Em), and G (255?C265 nm_Ex/435?C455 nm_Em). The analysis revealed that the reduction of DOM occurred mostly during the UASB treatment where most of the DOM reduction resulted from the removal of the HPOA and HPIB fractions. The HPOA fraction, a group of humic-like substances, is of particular concern when reclaiming treated brewery wastewater, and although it was reduced by more than 80% of its initial amount, it was still a dominant DOM fraction in the effluents.     

Study of personal–indoor–ambient fine particulate matters among school communities in mixed urban–industrial environment in India

A sampling program was conducted to investigate the formation of disinfection by-products (DBPs) and dissolved organic carbon (DOC) at two advanced water treatment plants in Kaohsiung City, Taiwan. The results in this study can be used as a reference for the operational control of water treatment plants and the setting of regulations in Taiwan. Samples of drinking water were collected from two advanced water treatment plants from June 2007 to April 2008. Changes in the concentration of dissolved organic carbon, the trihalomethane formation potential, and the haloacetic acids formation potential were measured in raw water samples. Variations in the concentrations of trihalomethanes (THMs) and haloacetic acids (HAA₅) in finished drinking water were evaluated. The major species of HAA₅ were in the order of dichloroacetic acid and trichloroacetic acid and the THM was of trichloromethane. DOC was strongly related to DBPs in raw water. In this investigation, the removal efficiency of DBPs in Plant A (ultrafiltration/reverse osmosis system) exceeded that in Plant B (ozonation/biological activated carbon system). Both advanced water treatment plants greatly improved the quality of drinking water.     

Investigation of trace elements in agricultural soils by BCR sequential extraction method and its transfer to wheat plants

In this study, soil samples were collected from Edirne, Turkey in both summer and winter seasons and subjected to the modified Community Bureau of Reference (BCR) sequential extraction procedure in order to investigate the chemical partitioning of metals in soils and to predict heavy metals uptake by wheat grains which grown at the same soils. The samples were subjected to a three stage extraction procedure proposed by the BCR. The three phases that were separated out in the following order: (1) carbonate, exchangeable, (2) Fe?CMn oxides, and (3) organic matter. Metal concentrations of soil fractions and grain samples were determined by inductively coupled plasma atomic emission spectroscopy. The wheat samples were prepared to analysis using microwave acid digestion procedure. The pseudo-total concentrations of metals were determined after aqua regia digestion. The analytical accuracy of the method was evaluated by using the Standard Reference Materials (BCR 142R Light Sandy Soil, NIST 2711 Montana Soil, and NIST 2704 Buffalo River Sediment). The sum of the metal contents obtained from the modified BCR sequential extraction procedure and pseudo-total metal contents for soil samples were used to calculate recovery values. In order to evaluate the bioavailability of metals, the relationships between the wheat-metal and soil-extractable metal concentrations were compared.     

Optimized Coagulation of High Alkalinity, Low Temperature and Particle Water: pH Adjustment and Polyelectrolytes as Coagulant Aids

The Yellow River in winter as source water is characterized as high alkalinity, low temperature and low particle concentrations, which have brought many difficulties to water treatment plants. This study fully examines the optimized coagulation process of the Yellow River by conventional and pre-polymerized metal coagulants, pH adjustment and polyelectrolytes as the primary coagulants or coagulant aids. For all the metal coagulants, polyaluminum chlorides are superior to traditional metal coagulants due to their stable polymeric species and low consumption of alkalinity. The removal of natural organic matter by monomeric metal coagulants can be improved through pH adjustment, which is in accordance with the higher concentration of polymeric species formed at corresponding pH value. With the addition of polyelectrolytes as coagulant aids, the coagulation performance is significantly improved. The effective removal of dissolved organic matter is consistent with high charge density, while molecular weight is relatively important for removing particles, which is consistent with polyelectrolytes as primary coagulants. These results suggest that the coagulation mechanisms in the removal of dissolved organic matter and particles are different, which may be exploited for optimized coagulation for the typical source water in practice.     

Preferential adsorption of fluorescing fulvic and humic acid components on activated carbon using flow field-flow fractionation analysis

Activated carbon treatment of drinking water is used to remove natural organic matter (NOM) precursors that lead to the formation of disinfection byproducts. The innate hydrophobic nature and macromolecular size of NOM render it amenable to sorption by activated carbon. Batch equilibrium and minicolumn breakthrough adsorption studies were performed using granular activated carbon to treat NOM-contaminated water. Ultraviolet (UV) absorption spectroscopy and flow field-flow fractionation analysis using tandem diode-array and fluorescence detectors were used to monitor the activated carbon sorption of NOM. Using these techniques, it was possible to study activated carbon adsorption properties of UV absorbing, fluorescing and nonfluorescing, polyelectrolytic macromolecules fractionated from the total macromolecular and nonmacromolecular composition of NOM. Adsorption isotherms were constructed at pH 6 and pH 9. Data were described by the traditional and modified Freundlich models. Activated carbon capacity and adsorbability were compared among fractionated molecular subsets of fulvic and humic acids. Preferential adsorption (or adsorptive fractionation) of polyelectrolytic, fluorescing fulvic and humic macromolecules on activated carbon was observed. The significance of observing preferential adsorption on activated carbon of fluorescing macromolecular components relative to nonfluorescing components is that this phenomenon changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the composition that existed in the aqueous phase prior to adsorption. Likewise, it changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the adsorbed phase. This research increases our understanding of NOM interactions with activated carbon which may lead to improved methods of potable water production.     

呼伦贝尔地区草原表层土壤中总有机碳与有机质初探

通过非分散红外线吸收法测定呼伦贝尔地区具有代表性的16个草原表层土壤(0~20 cm)中总有机碳、溶解性有机碳,使用重铬酸钾容量法测定有机质,并对其总有机碳与有机质水平及两者相关性进行了分析。初步分析了造成各样品之间总有机碳水平差异的原因。结果表明,只以打草场作为利用方式的土壤总有机碳含量较常年放牧场的总有机碳含量高。从草原类型和土壤类型上看,草甸草原总有机碳含量明显高于典型草原,黑钙土总有机碳含量明显高于栗钙土。综上,过度放牧会使草原土壤总有机碳大量释放。总有机碳含量与有机质含量有显著正相关性,相关系数达到0.902。     

Effects of salinity and organic matter on the partitioning of perfluoroalkyl acid (PFAs) to clay particles

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.