Nickel speciation in the presence of different sources and fractions of dissolved organic matter

This study evaluated nickel (Ni) speciation in the presence of different fractions (humic acid (HA), fulvic acid (FA)) and sources (natural sediment, Suwannee River, peat moss) of dissolved organic matter (DOM) at Ni concentrations toxicologically relevant to the freshwater amphipod, Hyalella azteca. The free Ni ion, Ni(2+), was measured in reconstituted water (with or without DOM) using a miniaturized ion-exchange technique (IET). Ni speciation from these experiments was compared to calculated results obtained from equilibrium modelling (WHAM, Model VI). While it is known that Ni will complex with DOM, it was found that under acutely toxic Ni exposure concentrations ([Ni(Total)]=5mg/L, or 85.1 microM) representative surface-water DOC concentrations ( approximately 10mg/L) played little or no role in Ni speciation. Conversely, at sublethal Ni exposure concentrations ([Ni(Total)]=0.2 and 0.5 microg/L, or 3.4 and 8.51 microM, respectively) DOM significantly affected Ni speciation with [Ni(2+)] decreasing with increasing concentration of DOM. It was found that for similar concentrations of DOC (same fraction, different sources), the measured Ni(2+) concentrations were reduced (relative to the control), but similar to one another. Conversely, at similar DOC concentrations, the HA fraction reduced Ni(2+) levels to a greater extent than the associated FA fraction. Overall, this study provides proof of principle that Suwannee River and peat humic substances are suitable analogues for natural sediment pore-water DOM when evaluating Ni bioavailability in freshwater.     

Characterization,DBPs formation,and mutagenicity of different organic matter fractions in two source waters

Dissolved organic matters (DOM) are critical in the formation of the mutagenic disinfection byproducts (DBPs). In this study, five DOM fractions were isolated and investigated from a contaminated river and a clean reservoir source waters using resin adsorption. The DOM fractions were characterized with excitation–emission matrix, and several typical DBPs formation potentials and the mutagenicity of each DOM fraction were measured. Among these fractions, hydrophobic neutrals (HON), hydrophilic acids (HIA) and hydrophilic bases (HIB) generated the highest carbon-containing DBPs in the river source water, as did HIB and hydrophobic bases (HOB) in reservoir water. Hydrophobic acids (HOA), HON, and HIA were the three most important fractions forming nitrogen-containing DBPs. Following chlorination, the mutagenicity of HON, HIA, HOA and HIB was 1503, 626, 422 and 116 ng 4-NQO/mg DOC in river water, respectively. Only HIA and HOA were mutagenic with 85 and 10 ng 4-NQO/mg DOC in reservoir water, respectively. The soluble microbial products like substances and aromatic proteins contributed significantly to the mutagenicity of river water; whereas the humic acid-like and fulvic acid-like substances were the primary contributors to the mutagenicity of reservoir water.     

Effects of dissolved organic carbon concentration and source, pH, and water hardness on chronic toxicity of copper to Daphnia magna

The effects of pH (5.3-8.7), water hardness (CaCO3 at 25-500 mg/L), dissolved organic carbon (DOC) concentration (1.6-18.4 mg/L), and DOC source on the chronic toxicity of copper to Daphnia magna were investigated by using a multifactorial, central composite test design. Natural dissolved organic matter (DOM) was collected at three sites in Belgium and The Netherlands by using reverse osmosis. For a total number of 35 toxicity tests performed, 21-d no-observed-effect concentrations (NOECs) of copper based on reproduction ranged from 29.4 to 228 microg/L and 21-d concentrations of copper causing 50% reduction of reproduction (EC50s) ranged from 41.5 to 316 microg/L. Statistical analysis revealed that DOC concentration and pH had a significant effect on copper toxicity but hardness (at the levels tested) did not. In general, an increase in pH or DOC resulted in a linear increase of 21-d NOEC and EC50 values. All DOMs (originating from three different sources) reduced copper toxicity to the same extent. Multiple linear regression analysis on the results of all 35 toxicity tests revealed that DOC concentration is the most important factor for chronic toxicity of copper to D. magna, explaining about 60% of the observed variability, whereas pH only explained about 15% of the observed variability. Regression models were developed (with DOC and pH as parameters) that were capable of predicting NOECs and EC50s within a factor of 1.9 from observed NOEC and EC50 values obtained with eight natural surface waters spiked with copper. Until future research further elucidates the mechanisms underpinning the observed bioavailability relations, these empirical regression models can become a first simple tool for regulatory applications.     

Influence of Dissolved Organic Matter on Acute Toxicity of Zinc to Larval Fathead Minnows (Pimephales promelas)

We conducted laboratory toxicity tests in support of the development of a biotic ligand model (BLM) to predict acute toxicity of zinc (Zn) to fathead minnows (Pimephales promelas). To test the effect of dissolved organic matter (DOM) on Zn toxicity, we exposed larval fathead minnows to Zn in water containing elevated concentrations of dissolved organic carbon (DOC) in 96-h static-renewal toxicity tests. We tested DOM isolated from four surface waters: Cypress Swamp, Delaware; Edisto River, South Carolina; Suwannee River, Georgia; and Wilmington, Delaware, wastewater treatment effluent. The DOM isolates from the Edisto River and Wilmington wastewater treatment effluent contained elevated concentrations of NaCl (20–110× control NaCl) due to the use of a Na⁺-exchange resin to remove Ca²⁺ and Mg²⁺ during the DOM isolation process. Therefore, we also performed Zn toxicity tests in which we added up to 20 mM NaCl to exposure solutions containing Cypress Swamp and Suwannee River DOM. A threshold concentration of 11 mg DOC/L was needed to decrease Zn toxicity, after which the 96 h Zn LC50 was positively correlated with DOC concentration. Elevated NaCl concentrations did not alter Zn toxicity in the presence of DOM. In conjunction with data from other studies with fish and invertebrates, results of this study were used to calibrate Version 2.1.1 of the Zn BLM. BLM-predicted LC50s for our exposure waters containing elevated DOM concentrations were within the range of acceptable deviation relative to the observed LC50s (i.e., 0.5–2× observed LC50s); however, BLM-predicted LC50s for our exposure waters containing < 1 mg DOC/L were 2–3× lower than the observed LC50s (i.e., the BLM over-predicted the toxicity). Therefore, the current composite-species BLM for Zn could be improved for fathead minnows if that species were modeled separately from the other species used to calibrate Version 2.1.1.     

UV-B-Induced acute toxicity of pyrene to the waterflea Daphnia magna in natural freshwaters

The effects of various water characteristics in natural freshwaters on the acute toxicity of one polycyclic aromatic hydrocarbon (PAH), pyrene, to a pelagic invertebrate Daphnia magna was studied under ultraviolet B (UV-B) radiation and in the dark. Pyrene was photoactivated and was more toxic to D. magna in the presence of UV-B radiation. Dissolved organic material (DOM), measured as dissolved organic carbon (DOC), significantly reduced the photoenhanced toxicity of pyrene. Under UV-B radiation the EC(50) values were lower and in relation to the amount of DOM, ranging from 3.0 to 30.0 microg/L pyrene, whereas in the dark they were between 29.2 and 54.8 microg/L and not related to the amount of DOM in the waters. Although the condition and mortality of the daphnids in the control groups were not affected by UV-B irradiation, the increased toxicity was considered to be either an additive or a synergistic effect of both the photomodified pyrene and the stressing light conditions of UV-B. The measured binding of pyrene to DOM was low, although it was related to the amount of DOC. Despite the relatively high intensity of UV-B used, humic substances in the waters remained undegraded. It was thus concluded that with their brownish-yellowish color, waters rich in humic substances decreased the photomodification of the freely dissolved parent compound simply by diminishing the light penetration in these waters and, by implication, contact with the intact compound. These results suggest that DOM in surface waters plays an important role in protecting against the photoinduced toxicity of PAHs.     

Validation of a modified flory-huggins concept for description of hydrophobic organic compound sorption on dissolved humic substances

Sorption coefficients (K(DOC)) on dissolved organic matter (DOM) have been determined by means of solid-phase microextraction (SPME) for hydrophobic organic compounds (HOCs) of various classes, for example, polycyclic aromatic hydrocarbons (PAHs), noncondensed arenes, and alkanes. Relating the K(DOC) values obtained to the octanol-water partition coefficients of the solutes results in class-specific correlations. Obviously, PAHs have a higher affinity to DOM than other HOCs with equal K(OW) values. The different K(DOC) to K(OW) correlations can be combined into one general formula based on a modified Flory-Huggins concept. It permits the calculation of sorption coefficients from the solubility parameters (delta) and K(OW) values of the solutes and the solubility parameter of the sorbent. The latter value, which is specific to the DOM under consideration, can be determined from a single measured sorption coefficient. By applying the proposed Flory-Huggins concept, which is based on the presumption of nonspecific interactions between HOCs and DOM, the different affinities of PAHs, noncondensed arenes, and alkanes to DOM can be accurately predicted.     

More than inorganic copper is bioavailable to aquatic mosses at environmentally relevant concentrations

The present study investigates how dissolved organic matter (DOM) alters copper bioavailability at environmentally relevant concentrations (1-5 microg/L of dissolved copper, 1-4 mg/L of dissolved organic copper). A methodology combining two biological endpoints (short-term and steady-state bioaccumulation of copper by the aquatic moss Fontinalis antipyretica) and a sampling of labile copper with diffusion gradient in thin films (DGT) is proposed for batch experiments conducted with mineral water and various DOM, ethylenediaminetetra-acetic acid (EDTA), humic acid, and natural Seine River (France) extracts (hydrophobic and transphilic fractions). All types of DOM reduce the bioavailability of copper to aquatic mosses, and this reduction was more pronounced for the short-term biological endpoint, which was taken as being representative for environmental exposure. Labile copper sampled with DGT made it possible to estimate short-term bioaccumulation in the case of EDTA and natural Seine River extracts. With humic acid solutions, however, labile copper was lower than bioavailable copper. This result suggests that at realistic metal concentrations and with certain types of natural DOM, bioavailable copper might comprise not only inorganic copper but also some weak organic complexes. Hence, labile copper, in situ sampled with DGT, might not systematically overestimate bioavailable copper, as suggested previously on the basis of in vitro toxicity studies.     

Binding interactions of 1-naphthol with dissolved organic matter of Lake Biwa and treated sewage wastewater: The role of microbial fulvic acid

The binding interactions of 1-naphthol with effluent and whole natural dissolved organic matter (DOM) samples were analyzed by using a fluorescence quenching technique. Nonfractionated DOM samples from Lake Biwa (Japan), creek water, treated sewage effluents, and an extracted Lake Biwa fulvic acid (LBFA) standard were used as quenchers and compared at the same 1-naphthol with DOM organic carbon ratios found for low natural dissolved organic carbon (DOC) levels (～4.5?mg/L). Natural and effluent DOM (eDOM) samples were characterized by the DOC level, relative hydrophobicity (RH%), ultraviolet (UV)-visible absorbance and fluorescence excitation emission spectroscopy. These parameters were compared with those of the reference LBFA standard. Concave-up Stern-Volmer plots accounted for both the partitioning and the adsorptive binding in the eDOM-polycyclic aromatic hydrocarbons (PAH) system as compared with the nonspecific partitioning in the natural DOM-PAH system. Strong linear regressions (r(2) >?0.80) between the log K(DOC) values, the RH%, the UV absorbances, and the Fl(340-435) -UV(340) indices for the structural composition and molecular weights of the DOM samples were obtained. These results suggest that low molecular weight microbial fulvic acid (<800 Da) is dominant in the eDOM-PAH binding interactions, as well as in the distinct molecular structure of the eDOM samples, which resulted in fivefold to sixfold higher binding magnitude for 1-naphthol than for the other samples. Environ. Toxicol. Chem. 2012; 31: 2201-2209. ? 2012 SETAC.     

The evaluation for alterations of DOM components from upstream to downstream flow of rivers in Toyama (Japan) using three-dimensional excitation-emission matrix fluorescence spectroscopy

The dissolved organic matter (DOM) is one of the important factors for controlling water quality. The behavior and constitutions of DOM is related to the risk of human health because it is able to directly or indirectly affect the behavior, speciation and toxicity of various environmental pollutants. However, it is not easy to know the contents of DOM components without using various complicated and time consuming analytical methods because DOM is a complex mixture and usually exists at low concentration. Here, we describe the fluorescence properties of DOM components in water samples collected from four rivers in Toyama, Japan by means of the three-dimensional excitation-emission matrix (3DEEM) fluorescence spectroscopy. In order to evaluate the alterations of DOM components in each of the river during the flow from upstream to downstream, the patterns of relative fluorescence intensity (RFI) at six peaks which are originated from fluorophores including humic-like and protein-like components were investigated. The changes in the patterns of RFI values at each of the peak and the concentration of dissolved organic carbon (DOC) for each river water sample were discussed in connection with the differences of land use managements and basic water quality parameters, such as pH, EC, turbidity, Fe(3+), T-N, NO(3)-N, T-P, PO(4)-P, chlorophyll a, DOC and N/P ratio. The DOC concentrations in the water samples collected from these rivers were relatively low (0.63-1.16 mg/L). Two main peaks which have a strong RFI value expressed a positive correlation with the DOC concentration (r = 0.557, 0.535). However, the correlations between the RFI values for other four peaks and the DOC concentration were below 0.287. The alterations of DOM components during the flow of a river from upstream to downstream were investigated from the changes in the patterns of RFI values for six fluorescent peaks. It was clarified that the great increase of RFI values in peak A and peak T from river water located in urban area showed high concentration of PO(4)-P and Fe(3+), and low N/P ratio due to the high biological activities. The values of fluorescence index (FIX) and biological index (BIX) were as high as 1.60 and 0.72, respectively.     

The ability of dissolved organic matter (DOM) to influence benzo[a]pyrene bioavailability increases with DOM biodegradation

The biodegradation of two substrates and the ability of dissolved organic matter (DOM) to influence benzo[a]pyrene bioavailability as DOM biodegradation progressed were monitored in reactors. Substrates were composed of algae extracts and an artificial substrate that mimics raw wastewater, which were considered to be autochthonous and anthropogenic allochthonous models for DOM, respectively. The soluble microbial products formed during biomass activity were also studied. The aromaticity of DOM was investigated with specific ultraviolet absorbance. Partitioning coefficients between DOM and benzo[a]pyrene, K(DOC)(biol), were biologically determined by means of 4-h bioaccumulation experiments on Daphnia magna. Parent and degraded substrates always significantly reduced the bioaccumulation of benzo[a]pyrene at environmental DOM concentrations. Soluble microbial products also significantly affected the benzo[a]pyrene bioaccumulation. K(DOC)(biol) ranged between 2 x 10(4) and 4 x 10(5) L/kg. As the artificial wastewater biodegraded, DOM aromaticity increased, as did K(DOC)(biol). During the biodegradation of algae extract DOM, K(DOC)(biol) increased, whereas their aromaticity slightly decreased.     

Development of negligible depletion hollow fiber-protected liquid-phase microextraction for sensing freely dissolved triazines

A new sampling method, termed negligible depletion hollow fiber-protected liquid-phase microextraction, was developed for sensing the freely dissolved concentration (C(free)) and evaluating the availability of atrazine (ATR), desethyl atrazine (DEA), and simazine (SIM) in water. The sampling device was prepared by impregnating 1-octanol to both the pores and the lumen of a piece of polypropylene microporous hollow fiber membrane. After equilibrium and negligible depletion extraction, the 1-octanol in the lumen of the hollow fiber (10 microl) was collected for determination of triazines. Determination of C(free) and the distribution coefficient to 1-octanol (D(ow)) can be performed with this technique. A wide linear working range (1-200 microg/L) and low detection limits (0.1-1 microg/L) were obtained for triazines. Measured log D(ow) values of DEA (1.44 +/- 0.04), SIM (2.06 +/- 0.06), and ATR (2.33 +/- 0.05) agreed well with those reported in the literature. The measured D(ow) values were independent of the chemical concentration and sample pH (pH 3-10) and negligibly affected by the sample salinity (0-500 mM), suggesting that environmentally relevant pH and salinity have no significant effects on the availability of triazines. Although a slight (< or = 31%) increase of C(free) was observed, one-way analysis of variance indicated the C(free) of triazines were not significantly affected by the presence of Aldrich humic acid, Acros humic acid, and bovine albumin V (dissolved organic carbon [DOC], 0-100 mg/L). From 3 to 36% of the spiked triazines, however, were found to associate with the dissolved organic matter (DOM) in surface-water samples (DOC, 32.0-61.9 mg/L), suggesting the origin of the DOM is a key parameter in determining its association with and, thus, the availability of triazines.     

Influence of dissolved organic matter source on silver toxicity to Pimephales promelas

In the environment, the formation of organic and inorganic silver complexes can decrease Ag bioavailability (toxicity) to aquatic organisms. However, current water quality regulations do not consider the protective effects of water quality parameters such as dissolved organic carbon (DOC) concentration. To determine the effect of DOC concentration and source on silver toxicity, nine different natural organic matter isolates were used in 96-h static-renewal toxicity tests with fathead minnow (Pimephales promelas). The 96-h dissolved silver median lethal concentrations (LC50) among different sources of dissolved organic matter varied by up to fivefold (4.5-23.3 microg/L). Further, toxicity tests with organic matter from the site with the lowest 96-h LC50 value suggested only limited additional attenuation of silver toxicity when DOC concentration was increased from 5.1 to 14.0 mg/L. With this site excluded, we found little more than a twofold difference among 96-h dissolved Ag LC50s for the remaining sources (10.1-23.3 microg/L). However, significant toxicological differences among sites remained. It was apparent that organic matter from different sources varied both chemically and toxicologically, but no conclusions could be drawn that related compositional variation to observed Ag toxicity for these isolates.     

Measuring the bioavailability of two hydrophobic organic compounds in the presence of dissolved organic matter

Bioavailability of benzo[a]pyrene (BaP) and 3,3',4,4'-tetrachlorobiphenyl (TCB) was studied in natural lake water containing dissolved organic matter (DOM). Lake water was diluted to give a dissolved organic carbon (DOC) range of 1 to 20 mg/L. Partition coefficients for the model compounds were assessed at different DOM concentrations and over time with three different methods, namely equilibrium dialysis and reverse-phase and liquid-liquid extraction. In addition, biological partition coefficients were estimated from the difference in the bioconcentration of the model compounds in Daphnia magna in the presence and absence of DOM. Results showed that bioavailability of the model compounds was reduced by the presence of DOM. The equilibrium dialysis method gave the best estimates for bioavailability of the model compounds when compared with biologically determined values. Both the reverse-phase and the liquid-liquid extraction overestimated the bioavailable fraction. The more pronounced overestimation of bioavailable fraction of TCB suggested that the sorption of TCB was not only lower but the interaction was also weaker than that of BaP. Increasing DOM concentration produced lower partition coefficients and the effect seemed to be more pronounced when measured by the reverse-phase and the extraction methods.     

Effect of dissolved organic matter of various origins and biodegradabilities on the bioaccumulation of polycyclic aromatic hydrocarbons in Daphnia magna

As a preliminary study of the influence of urban organic matter on the bioavailability of polycyclic aromatic hydrocarbons (PAHs), the effect of different types of dissolved organic matter (DOM) on the bioaccumulation of fluoranthene, pyrene, or benzo[a]pyrene in Daphnia magna was studied. Commercial humic substances, DOM from the aeration basin of a wastewater treatment plant, and highly biodegradable DOM (algae or animal extracts) were tested. The bioaccumulation of benzo[a]pyrene was reduced by each DOM (up to 80% reduction with humic substances). Pyrene bioaccumulation was also decreased by each DOM to a lesser extent. Fluoranthene bioaccumulation was affected by the presence of humic acids only. In each experiment, the solution containing humic DOM led to the lowest bioaccumulation. Supposing that only dissolved PAHs were bioavailable, the reduction of bioaccumulation allowed a biological estimate of the partition coefficients of DOM and PAH, K(DOC). The estimated coefficients were positively related to the aromaticity of DOM and negatively related to its biodegradability.     

Dissolved fraction of standard laboratory cladoceran food alters toxicity of waterborne silver to Ceriodaphnia dubia

The biotic ligand model (BLM) for the acute toxicity of cationic metals to aquatic organisms incorporates the toxicity-modifying effects of dissolved organic matter (DOM), but the default parameterization (i.e., assuming 10% of DOM is humic acid) does not differentiate DOM from different sources. We exposed a cladoceran (Ceriodaphnia dubia) to Ag in the presence of DOM from filtered YCT (standard yeast-Cerophyll(R)-trout chow food recommended by the U.S. Environmental Protection Agency [EPA] for cladocerans), from the Suwannee River (GA, USA; relatively little anthropogenic input), and from the Desjardins Canal in Hamilton (ON, Canada; receives treated municipal wastewater effluent). In all three treatments, the dissolved organic carbon (DOC) concentration was 2 mg/L (the concentration following addition of YCT slurry at the U.S. EPA-recommended volume ratio). The average 48-h median effects concentration (EC50) ratios for dissolved Ag in the presence and absence of DOM [i.e., (EC50 with DOM)/(EC50 without DOM)] were as follows: Suwannee River, 1.6; Desjardins Canal, 2.2; and YCT filtrate, 26.8. Therefore, YCT filtrate provided much more protection against Ag toxicity than that provided by DOM from the surface waters. The major spectral characteristic that differentiated YCT filtrate from the other two types of DOM was a strong tryptophan peak in the excitation- emission matrix for YCT. These results have important implications for interpreting Ag toxicity tests in which organisms are fed YCT, and they suggest BLM-calculated toxicity predictions might be improved by incorporating specific chemical constituents or surrogate indices of DOM. Another component of the protective effect against Ag toxicity, however, might be that the dissolved fraction of YCT served as an energy and/or nutrient source for C. dubia.     

Sources and Properties of Natural Organic Matter (NOM) in Water Along the Dongjiang River (the Source of Hong Kong’s Drinking Water) and Toxicological Assay of Its Chlorination By-Products

The Dongjiang River is the major source of the drinking water supply for Hong Kong and also other parts of the Pearl River Delta in China, and the deterioration in the water quality of this river and the excessive levels of trihalomethanes (THMs) in the tap water of some districts in Hong Kong have become a matter of public concern. The main objective of the present study is to investigate the distribution patterns of natural organic matter (NOM) and their association with THM production in the Dongjiang River. We examined the physicochemical and biological properties of the river water and the corresponding sediment elutriate collected from four sampling sites along the Dongjiang River from upstream to downstream and chlorination experiments were conducted. Algal bioassays were performed in order to test the chlorination effects. The results showed that: (1) upstream NOM was derived from terrestrial input, while that at mid- and downstream was most likely derived from phytoplankton; (2) phytoplankton is a major contributor to NOM in the sediments, whereas sediments seem to be the site for major microbial degradation of NOM, biogeochemical recycling of nutrients and a potential NOM pool for the overlaying water during sediment resuspension; (3) dissolved organic carbon (DOC) in surface water is a good indicator for THM production, whereas ultraviolet (UV) absorbance at 254 nm (UV₂₅₄) is a better predictor for THM formation in the elutriates; (4) the bioassay results showed that toxic compounds other than THMs in the chlorinated water are the major factors causing algal growth inhibition.     

Effects of using synthetic sea salts when measuring and modeling copper toxicity in saltwater toxicity tests

Synthetic sea salts are often used to adjust the salinity of effluent, ambient, and laboratory water samples to perform toxicity tests with marine and estuarine species. The U.S. Environmental Protection Agency (U.S. EPA) provides guidance on salinity adjustment in its saltwater test guidelines. The U.S. EPA suggests using commercial sea salt brands, such as Forty Fathoms (now named Crystal Sea Marinemix, Bioassay Grade), HW Marinemix, or equivalent salts to adjust sample salinity. Toxicity testing laboratories in Canada and the United States were surveyed to determine synthetic sea salt brand preference. The laboratories (n = 27) reported using four brands: Crystal Sea Marinemix (56%), HW Marinemix (22%), Instant Ocean (11%), and Tropic Marin (11%). Saline solutions (30 g/L) of seven synthetic sea salts were analyzed for dissolved copper and dissolved organic carbon (DOC) content. Brands included those listed above plus modified general-purpose salt (modified GP2), Kent Marine, and Red Sea Salt. The synthetic sea salts added from < 0.1 to 1.2 microg Cu/L to the solution. Solutions of Crystal Sea Marinemix had significantly elevated concentrations of DOC (range = 5.4-6.4 mg C/L, analysis of variance, Tukey, alpha = 0.05, p < 0.001) while other brands generally contained < 1.0 mg C/L. The elevated DOC in Crystal Sea Marinemix was expected to reduce copper toxicity. However, the measured dissolved copper effective concentration 50% (EC50) for Crystal Sea Marinemix was 9.7 microg Cu/L, similar to other tested sea salts. Analysis indicates that the organic matter in Crystal Sea Marinemix differs considerably from that of natural organic matter. On the basis of consistently adding little DOC and little dissolved copper, GP2 and Kent Marine are the best salts to use.     

Organic carbon biostimulates rapid rhizodegradation of perchlorate

Previous hydroponics and field studies identified phytodegradation and rhizodegradation as the two main mechanisms by which plants metabolize perchlorate. Plant uptake and phytodegradation of perchlorate is a slower and undesired process that poses ecological risks resulting from phytoaccumulation of some fraction of the perchlorate. Meanwhile, rhizodegradation is a more rapid and favored process involving perchlorate-degrading bacteria utilizing dissolved organic carbon (DOC) as a carbon and energy (electron) source to rapidly degrade perchlorate to innocuous chloride. In the present study, rhizodegradation of perchlorate by willow trees (Salix nigra) was biostimulated using electron sources obtained from natural and artificial carbon sources. In bioreactors provided with carbon sources as 500 mg/L DOC, 25 to 40 mg/L of initial perchlorate concentrations were removed to below the ion chromatography method detection limit of 2 microg/L in approximately 9 d. For planted controls provided with no electron donors, the time required for the complete removal of the same doses of perchlorate was up to 70 d. Enhancement of rhizodegradation by organic carbon reduced the phytoaccumulated fraction of perchlorate by an order of magnitude from approximately 430 to 20 mg/kg. The implication of the present study is that the high fraction uptake and phytoaccumulation of perchlorate in agricultural products and the recycling of perchlorate into the ecosystem can be significantly curtailed by supplying electron donors derived from organic carbon sources to the root zone of plants.     

Development and field validation of a predictive copper toxicity model for the green alga Pseudokirchneriella subcapitata

In this study, the combined effects of pH, water hardness, and dissolved organic carbon (DOC) concentration and type on the chronic (72-h) effect of copper on growth inhibition of the green alga Pseudokirchneriella subcapitata were investigated. Natural dissolved organic matter (DOM) was collected at three sites in Belgium and The Netherlands using reverse osmosis. A full central composite test design was used for one DOM and a subset of the full design for the two other DOMs. For a total number of 35 toxicity tests performed, 72-h effect concentration resulting in 10% growth inhibition (EbC10s) ranged from 14.2 to 175.9 micrograms Cu/L (factor 12) and 72-h EbC50s from 26.9 to 506.8 micrograms Cu/L (factor 20). Statistical analysis demonstrated that DOC concentration, DOM type, and pH had a significant effect on copper toxicity; hardness did not affect toxicity at the levels tested. In general, an increase in pH resulted in increased toxicity, whereas an increase of the DOC concentration resulted in decreased copper toxicity. When expressed as dissolved copper, significant differences of toxicity reduction capacity were noted across the three DOM types tested (up to factor 2.5). When expressed as Cu2+ activity, effect levels were only significantly affected by pH; linear relationships were observed between pH and the logarithm of the effect concentrations expressed as free copper ion activity, that is, log(EbC50Cu2+) and log(EbC10Cu2+): (1) log(EbC50Cu2+)= - 1.431 pH + 2.050 (r2 = 0.95), and (2) log(EbC10cu2+) = -1.140 pH -0.812 (r2 = 0.91). A copper toxicity model was developed by linking these equations to the WHAM V geochemical speciation model. This model predicted 97% of the EbC50dissolved and EbC10dissolved values within a factor of two of the observed values. Further validation using toxicity test results that were obtained previously with copper-spiked European surface waters demonstrated that for 81% of tested waters, effect concentrations were predicted within a factor of two of the observed. The developed model is considered to be an important step forward in accounting for copper bioavailability in natural systems.     

Effect of dissolved organic matter on the growth of algae, Pseudokirchneriella subcapitata, in Korean lakes: the importance of complexation reactions

The objective of this study was to investigate the effect of dissolved organic ligands, such as EDTA, humic acids, hydrophobic and hydrophilic fractions of dissolved organic matter (DOM), on the growth of Pseudokirchneriella subcapitata in cultured media and natural lake waters. The growth of algae was gradually increased on the addition of dissolved organic ligands, but markedly declined at high concentrations, due to reduced bioavailable iron concentrations (e.g., Fe3+ and Fe'--inorganic ferric iron). The results demonstrated that the high growth rates of P. subcapitata were correlated with the hydrophobic, but not hydrophilic, DOM from five lakes, spiked under the nutrients-controlled conditions. This was attributed to the role of DOM in controlling the bioavailable iron due to complexation of Fe(III) with -COOH and -OH functional groups on the hydrophobic DOM. Therefore, the hydrophobic DOM, as chelating agent, is a biologically important component in the lake waters, which affects the algal growth by interacting with bioavailable iron in the lake water and can change the results of bioassay experiments.