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.     

Impact of irreversible sorption of phthalate acid esters on their sediment quality criteria

The equilibrium partitioning (EqP) method has been applied to establish sediment quality criteria (SQC); however, it does not consider the nonlinear irreversible sorption of many organic contaminants. In this research, the sorption and desorption of two phthalate esters (PAEs), dimethyl phthalate (DMP) and di(2-ethylhexyl) phthalate (DEHP), in four natural sediments collected from the Yangtze River and the Yellow River were studied; the impact of irreversible sorption of DMP and DEHP on SQC has been evaluated. Based on the reversible and irreversible biphasic sorption model, the values of maximum irreversible sorption capacity (q(max)(irr)) were 125.19 μg g(-1)-337.37 μg g(-1) for DMP and 515.87 μg g(-1)-591.40 μg g(-1) for DEHP. The q(max)(irr) value was positively related to the organic carbon and black carbon contents, cation exchange capacity, and surface area of the sediments. The values of the irreversible sorption coefficient K(oc)(irr) for both DEHP and DMP in the four sediments approximated to a constant of 10(6.46 ± 0.38), which was 1-2 orders of magnitude higher than their reversible sorption coefficient K(oc)(irr). The values of SQC for PAEs based on the EqP method were modified by involving the irreversible sorption. The modified SQC of DEHP could be 2 to 20 times higher than the value predicted by the EqP method, and the assessment results for DEHP contamination in the sediments with the modified SQC were more reasonable than those with the non-modified SQC. It indicated that the current SQC based on the EqP method may be unnecessarily strict for specific organic compounds and the irreversible sorption should be taken into account.     

Distribution and partition of polycyclic aromatic hydrocarbon in surface water of the Pearl River Estuary, South China

Water samples were collected in the Pearl River Estuary in July 2002 and April 2003. The particulate and dissolved phase polycyclic aromatic hydrocarbons (PAHs) were determined. Total PAH concentrations in water samples were higher in April of 2003 (C (p): 4.0-39.1 ng/L or 445.1-1,089.9 ng/g; C (w): 15.9-184.2 ng/L) than in July of 2002 (C (p): 2.6-26.6 ng/L or 297.7-1,336.6 ng/g; C (w): 12.9-28.3 ng/L). It was found that 5, 6-ring PAHs enrich in the inner estuary samples and so did 3-ring PAHs in the July samples. Compositional differences in the suspended particulate matter (SPM) might be responsible for this observation. The partition coefficient (K (p)) increased with the increasing of the particular organic carbon content of suspended particles as well as the salinity of water, decreased with the increase of the total suspended particles content of samples. A linear correlation between logK (OC) and logK (OW) was found in two sampling periods. The observed values of logK (OC) exceed their predicted values derived form linear free energy relationship between logK (oc) and logK (ow), which could be attributed to the nonlinear sorption of soot-like carbons in suspended particles.     

Effects of pH and low molecular weight organic acids on competitive adsorption and desorption of cadmium and lead in paddy soils

The bioavailability and ultimate fate of heavy metals in the environment are controlled by adsorption-desorption process. Batch equilibrium experiments were performed to assess the effects of pH and low molecular weight organic acids (LMWOAs) on competitive adsorption and desorption of cadmium and lead in paddy soils from China. The results indicated that both soils exhibited greater sorption capacity for lead (Pb) (1.37-1.61-fold) than cadmium (Cd) as estimated by the maximum sorption parameter (Q) from the Langmuir equation. The Langmuir bonding energy coefficient (b) and distribution coefficient (K (d)) were greater for Pb than for Cd, furthermore, b (binary) and K (d) (single) were greater than b (single) and K (d binary), indicating that competition for sorption sites promote the retention of both metals on more specific sorption sites. Both Cd and Pb desorption as a function of solution pH was characteristic of "S" pattern. The presence of LMWOAs inhibited Cd or Pb desorption at the low concentrations (≤0.1 mmol L(-1)) but promoted Cd and Pb desorption at higher concentrations (≥0.5 mmol L(-1) for citric acid and ≥1 mmol L(-1) for malic and oxalic acid). The two paddy soils had a greater d (Cd) than d (Pb) in the presence of LMWOAs, indicating that Cd desorption was more affected by the presence of LMWOAs in binary metal system.     

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.     

Assessment on the distribution and partitioning characteristics of polycyclic aromatic hydrocarbons (PAHs) in Lake Baiyangdian, a shallow freshwater lake in China

The characteristics of polycyclic aromatic hydrocarbons (PAHs) in water, suspended particulate matter (SPM), sediments, and hydrophytes from Lake Baiyangdian, a shallow freshwater lake in China were studied. The low-molecular-weight PAHs (2-3 ring PAHs) predominated (61.2 to 84.5%) in all samples. Principal component analysis (PCA) of individual PAHs and the ratios of selected PAHs showed that the PAHs in the lake were mainly petrogenic inputs. The solid-liquid distribution coefficient (K(d)) in the water phase was much higher than the bioconcentration factor (BCF), and the leaf concentration factor (LCF) was higher than the root concentration factor (RCF) and stem concentration factor (SCF) in plant-sediment phase. Good linear log/log relationships were observed between the equilibrium partitioning coefficient (K(oc)) and the octanol-water partitioning coefficient (K(ow)), between RCF and K(ow), and between LCF and the octanol-air partitioning coefficient (K(oa)). These results indicated that PAHs accumulated more easily in SPM than in submerged aquatic plants, and some low-molecular-weight PAHs could accumulate and be translocated in the lake's media. Media characteristics, contamination sources, and physicochemical properties all affect the partitioning of PAHs among water, SPM, sediments, and hydrophytes.     

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.     

BDE-47在土壤矿物质与有机质上的吸附解吸特征

以多溴联苯醚典型单体2，2′，4，4′?四溴联苯醚（BDE?47）为研究对象，阐明了其在土壤矿物质与有机质上的吸附解吸行为及特征。结果表明：土壤中无机矿物质对BDE?47的吸附贡献不大，而有机质是调控BDE?47在土壤中吸附行为的关键组分；有机质对BDE?47的吸附能力与其有机碳含量和物理化学特性相关；BDE?47在腐殖酸上的解吸存在显著的滞后现象。     

Occurrence and sorption properties of arsenicals in marine sediments

The content of total arsenic, the inorganic forms: arsenite (As(III)) and arsenate (As(V)), the methylated forms: monomethylarsonic acid and dimethylarsinic acid (DMA), trimethylarsenic oxide, tetramethylarsenonium ion and arsenobetaine was measured in 95 sediment samples and 11 pore water samples from the Baltic Sea near the island of Bornholm at depths of up to 100 m. As(III+V) and DMA were detected in the sediment and As(III+V) was detected in the sediment pore water. Average total As concentration of 10.6?±?7.4 mg/kg dry matter (DM) in the sediment corresponds to previously reported values in the Baltic Sea and other parts of the world. Existing data for on-site measurements of sorption coefficients (Kd) of arsenicals in marine and freshwater sediments show large variability from <1 to >1,000 L/kg. In this work, calculated sorption coefficients (Kd and Koc) for As(III+V) showed significant correlation with depth, dissolved oxygen (DO), salinity and sediment classification; for depths <70 m, salinity <11 %, DO >9 mg/L and sand/silt/clay sediments the Kd was 118?±?76 L/kg DM and for depths >70 m, salinity >11 %, DO?<?9 mg/L and muddy sediments the Kd was 513?±?233 L/kg DM. The authors recommend using the found Kd value for arsenic in marine sediments when conditions are similar to the Baltic Sea. At locations with significant anthropogenic point sources or where the local geology contains volcanic rock and sulphide mineral deposits, there may be significantly elevated arsenic concentrations, and it is recommended to determine on-site Kd values.     

Visualising the equilibrium distribution and mobility of organic contaminants in soil using the chemical partitioning space

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.     

Distribution coefficients (K d) of stable iodine in estuarine and coastal regions, Japan, and their relationship to salinity and organic carbon in sediments

The sediment–water distribution coefficient, K _d, is one of the most important parameters in radionuclide assessment models. In this study, we determined K _ds of stable iodine (I) in estuarine and coastal regions. We studied 16 estuarine and coastal regions of Japan and obtained I data on water and sediments. Data on salinity, pH, dissolved organic carbon and dissolved oxygen in water, and organic carbon (OC) in sediments were also obtained as estuarine variables. Determined K _ds of I in the Sagami River estuary decreased along the salinity gradient (salinity range, 0.1–33.8), indicating that salinity is one of the important factors controlling the K _d values; however, when the K _d values were compared among all the estuaries, the difference between minimum and maximum K _d values varied by about two orders of magnitude in a narrow salinity range of 30.0–34.4. A significant correlation between K _d value and OC content in sediments was observed in all the stations with a salinity of ≥30 except for stations in the Ishikari and Onga River estuaries. The exceptions are probably due to different sources of the sediments, which are explained by the results of relatively low I/OC ratios in sediments in those two estuaries, compared to the other estuaries. Thus, OC in sediments as well as salinity may be responsible for the variation of K _ds of I in the estuarine and coastal regions.     

Competitive sorption of Cd, Cu, Mn, Ni, Pb and Zn in polluted and unpolluted calcareous soils

The objectives of this study were to investigate competitive sorption behaviour of heavy metals (Cd, Cu, Mn, Ni, Pb and Zn) under different management practices and identify soil characteristics that can be correlated with the retention and mobility of heavy metals using 65 calcareous soil samples. The lowest sorption was found for Mn and Ni in competition with the other metals, indicating the high mobility of these two cations. The Freundlich equation adequately described heavy metals adsorption. On the basis of Freundlich distribution coefficient, the selectivity sequence of the metal adsorption was Cu?>?Pb?>?Cd?>?Zn?>?Ni?>?Mn. The mean value of the joint distribution coefficient (K _dΣsp) was 182.1, 364.1, 414.7, 250.1, 277.7, 459.9 and 344.8 l kg^?1 for garden, garlic, pasture, potato, vegetables, wheat and polluted soils, respectively. The lowest observed K _dΣsp in garden soil samples was due to the lower cation exchange capacity and lower carbonate content. The results of the geochemical modelling under low and high metal addition indicated that Cd, Ni, Mn and Zn were mainly retained via adsorption, while Pb and Cu were retained via adsorption and precipitation. Stepwise forward regression analysis showed that clay, organic matter and CaCO₃ were the most important soil properties influencing competitive adsorption of Cd, Mn, Ni and Zn. The results in this study point to a relatively easy way to estimate distribution coefficient values.     

Sorbed metals fractionation and risk assessment of release in river sediment and particulate matter

Fractionation of metals in natural sediment and suspended particulate matter (SPM) of Tadjan River is investigated. Competitive sorption, sorption capacities of sediment and SPM as well as fractionation of metal-loaded sediment and SPM are also examined. A risk assessment code (RAC) is applied to estimate the risk of heavy metals release into the environment during the sorption process. Results revealed that sediments and SPM containing more than 25 % of clay minerals and higher amounts of calcite have great capacity of metal sorption, particularly for Cu, Ni, and Mn. Assessing the risk of metals release prior to and following sorption tests indicates that RAC of metals would significantly increase from the level of no or low risk in natural sediment and SPM to high or very high risk after sorption. The Langmuir model reveals that the highest affinity for Cu, Mn, and Ni in sediment is the organic fraction. The classic isotherm models of Freundlich and Langmuir can fit the data from chemical extraction studies of adsorbed metals, indicating that although sorption was apparently a physical and chemical process in the river, isotherm models can be used to simulate the sorption and accumulation in different geochemical phases within the particulate matter.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.     

Adsorption of domoic acid to marine sediments and clays

Conditional solid-water distribution coefficients (K(d)) for the adsorption of domoic acid (DA) to a series of complex sediments and clays were determined in artificial seawater. K(d) ranged from 5.11 L g(-1) to 0.97 L g(-1), with a corresponding ranking of: kaolinite > Gulf of Mexico sediment > Santa Barbara Basin sediment > Bread and Butter Creek sediment > poorly crystallized kaolin > Ca-montmorillonite > Na-montmorillonite > well crystallized kaolin > diatomaceous earth. Adsorption correlated with the anion exchange capacity of the clays tested (R(2) = 0.98), but not the more structurally complex sediments. The effect of added transition metals (Fe(iii), Cu(ii), Al(iii)) and terrestrially derived dissolved organic matter (Suwannee River DOM, SRDOM) on DA adsorption to Na-montmorillonite, well crystallized kaolin, and Gulf of Mexico sediment, was also tested. The addition of transition metals led to increased adsorption to all surfaces by a factor of 2-7, presumably by enabling the adsorption of DA-metal complexes. SRDOM enhanced DA adsorption by a factor of approximately 2.5. The release of adsorbed DA from sediments was also examined. Under our conditions, adsorbed DA equilibrated with the overlying aqueous phase within minutes with approximately 50% release.     

Adsorption study of 14C-paraquat in two Malaysian agricultural soils

The adsorption equilibrium time and effects of pH and concentration of ¹⁴C-labeled paraquat (1,1^??-dimethyl-4,4^??-bipyridylium dichloride) in two types of Malaysian soil were investigated. The soils used in the study were clay loam and clay soils from rice fields. Equilibrium studies of paraquat in a soil and pesticide solution were conducted. Adsorption equilibrium time was achieved within 2 h for both soil types. The amount of ¹⁴C-labeled paraquat adsorbed onto glass surfaces increased with increasing shaking time and remained constant after 10 h. It was found that paraquat adsorbed by the two soils was very similar: 51.73 (clay loam) and 51.59 ?? g g^???1 (clay) at 1 ?? g/ml. The adsorption of paraquat onto both types of soil was higher at high pH, and adsorption decreased with decreasing pH. At pH 11, the amounts of ¹⁴C-labeled paraquat adsorbed onto the clay loam and clay soil samples were 4.08 and 4.05 ?? g g^???1, respectively, whereas at pH 2, the amounts adsorbed were 3.72 and 3.57 ?? g g^???1, respectively. Results also suggested that paraquat sorption by soil is concentration dependent.     

Sorption of phthalate acid esters on black carbon from different sources

Black carbon (BC) is known as a strong sorbent for the sorption of planar hydrophobic organic compounds (HOCs), but there is very little information about the sorption of nonplanar HOCs on BC. In this study, the sorption of di-(2-ethyl-hexyl) phthalate (DEHP), one kind of nonplanar phthalate acid ester (PAE), by environmental BC collected from river sediments and pure BC (char-wood, char-stalk and soot-ash) was investigated. Strong and nonlinear sorption was observed for the sorption of DEHP on both pure BC and environmental BC with the Freundlich exponent ranging from 0.55 to 0.75 except for soot-ash, and the measured K(BC) (BC-water partition coefficient) of DEHP was about one order of magnitude higher than its organic carbon-water partition coefficient. There was a significant difference in sorption capacity among the environmental and pure BC. The presence of di-methyl phthalate (DMP) could significantly decrease the sorption of DEHP on BC, especially for environmental BC. In addition, the contribution of BC to the total sorption of DEHP on original river sediments was more than 50% when the equilibrium concentration of DEHP was less than 10 μg L(-1). This study indicated that ortho-substituted nonplanar PAEs could also be strongly sorbed by BC, and the difference in sorption among the BC samples revealed that it is important to take the source of BC into account when assessing its effects on the fate of HOCs in aquatic environment.     

Sorption of carbon tetrachloride,ethylene dibromide,and trichloroethylene on soil and clay

The sorption of carbon tetrachloride, ethylene dibromide, and trichloroethylene in two silty clay loam soils and aluminium (Al³⁺) or calcium (Ca²⁺) saturated montmorillonite clay was studied. When the adsorbents were exposed to environmental levels of these chemicals (10 to 1000 ppb in water) the amounts of each of the chemicals sorbed were 6% or less of that available except for a 17% sorption of trichloroethylene by Al-saturated clay. In the case of the Ca-saturated clay, there was no apparent sorption of carbon tetrachloride or trichloroethylene. When soil sorption was normalized based on the soil organic carbon content (K _oc) a correlation was found between the K _oc, water solubility, and octanol/water partitioning coefficients of the chemicals. However, carbon tetrachloride did not behave according to with the predicted relationships.