Mercury partition in the interface between a contaminated lagoon and the ocean: The role of particulate load and composition

After having estimated the patterns of flow to the ocean and found some seasonal and tidal differences, mainly with regard to the relative importance of dissolved and particulate fractions, mercury partitioning at the interface between a contaminated lagoon and the Atlantic Ocean was investigated during four tidal cycles in contrasting season and tidal regimes. Mercury was found to be located predominantely in the particulate fraction throughout the year, contributing to its retention within the system. Seasonal conditions, variations in marine and fluvial signals and processes affecting bed sediment resuspension influenced the character and concentration of suspended particulate matter in the water column. Variation in the nature, levels and partitioning of organic carbon in the particulate fraction affected levels of particulate mercury as well as mercury partitioning. These results highlight the dominant role of suspended particulate matter in the distribution of anthropogenic mercury and reinforce the importance of competitive behavior related to organic carbon in mercury scavenging.     

Real-time observation of dispersed hydrothermal plumes using nephelometry: examples from the Mid-Atlantic Ridge

As part of the 1984–1985 NOAA VENTS program on the Mid-Atlantic Ridge, nephelometry was used to provide real-time detection and tracking of dispersed hydrothermal plumes. At all nine 1984 study sites, hydrothermal activity was detected by in-situ, real-time nephelometer measurements and later confirmed by dissolved Mn and particulate Fe measurements. These same techniques were employed in a site-specific survey of the Trans-Atlantic Geotraverse (TAG) area in 1985 where large water-column anomalies in turbidity and in dissolved Mn helped lead to the discovery of high-temperature black smokers.The optical response of the nephelometer was to hydrothermally-derived particulate matter. Thus strong correlations existed between the nephelometer readings and total suspended matter (r = 0.98, n = 34), and particulate Fe (r = 0.88, n = 32). In addition, digital nephelometer data correlated well with dissolved Mn (r = 0.88; n = 78) throughout a large concentration range (0.2–31.0 nmol/kg).These data provide good evidence for the utility of in-situ nephelometer measurements for locating and surveying plumes from hydrothermal vents. It also appears possible, within limits, to predict concentrations of in-situ total suspended matter, of particulate Fe and of dissolved Mn.     

Reactivity of transparent exopolymeric particles: A key parameter of trace metal cycling in the lagoon of Nouméa, New Caledonia

Seawater samples were collected in the lagoon of Nouméa (New Caledonia) along two transects from coastal bays to the oligotrophic barrier reef. Dissolved (<0.2 μm) and sub-micrometer (0.2–0.8 μm) concentrations of chromium, nickel and zinc were measured. Concentrations in the 0.2–0.8 μm size range were correlated with transparent exopolymeric particles (TEP) turnover rates, suggesting that a TEP pool rapidly cycling in the system is more reactive toward metals. The role of TEP reactivity in the transfer efficiency of metals from dissolved to particulate phases was estimated through variations of the metal partitioning coefficient K between sub-micrometer TEP and solution, as a function of the water mass residence time. The log K (6.0–8.0) increased from high to low residence time, suggesting that TEP reactivity increases when water masses renew rapidly. This suggests that hydrodynamics control TEP reactivity toward metals. The characteristics (adsorption vs. complexation) of TEP-metal association are discussed.     

Environmental behavior of organotin compounds in the coastal environment of Xiamen,China

In 2006, organotins pollution were investigated in the coastal environment of Xiamen, China. Six species of organotin compounds including tributyltin, triphenyltin and their degradation compounds were quantified in the dissolved and particulate phases of the water, and in the sediment using GC-FPD. The concentrations of organotin compounds ranged from 2.2 to 160 ng (Sn) L⁻¹ dissolved in the water, 0.14–6.7 ng (Sn) L⁻¹ in suspended particulate matter and nd ∼ 26 ng (Sn) g⁻¹ (dry weight) in the sediment. The highest concentration of total organotin or tributyltin in water was found in a shipyard and at a station near the inlet of the harbor, indicating fresh inputs of antifouling paints to Xiamen’s coastal environment. Organotin speciation was performed on sediment cores to investigate contamination trends over the past ten years in the harbor. The results of ²¹⁰Pb dating indicated that Xiamen western harbor suffered contamination during 2000. The environmental behavior of organotins such as the enhancement of the microlayer, partitioning between water/suspended particulate matter and between water/sediment are also discussed in this paper.     

In-situ partitioning and bioconcentration of polycyclic aromatic hydrocarbons among water,suspended particulate matter,and fish in the Dongjiang and Pearl Rivers and the Pearl River Estuary,China

The partitioning and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in water, suspended particulate matter (SPM), and fish samples from the Dongjiang River (DR), Pearl River (PR), and the Pearl River Estuary (PRE) were examined. Although PAHs are much lower in PRE than in DR or PR, PAHs in some fish species are significantly higher in PRE than in DR or PR. Aqueous or particulate PAHs respectively show significant correlations with dissolved organic carbon, particulate organic matter, and chlorophyll a, suggesting that biological pumping effect regulates their distribution. The in situ partitioning coefficients (log K_oc) for PAHs are one order magnitude higher than the empirical log K_oc–log K_ow correlation. The bioconcentration factor (BCF) is slightly higher for the marine fish than for the freshwater fish. The above phenomena indicate that BCF may vary due to the diversity of fish species, feeding habits, and metabolism of PAHs in fish.     

Analytical and experimental study on dissolved pollutant wash‐off over impervious surfaces

Non‐point source pollution in the impervious surface of city, which including dissolved and particulate pollutants, is a significant source of water pollution. Simple first‐order decay models can generally simulate the cumulative wash‐off process of the particulate pollutants. There is inadequate knowledge as to whether or not they are suitable for dissolved pollutants. This study presents a mathematical wash‐off model for dissolved pollutants, which combines analytical equations for overland flows and the exponential equation for the pollutant wash‐off. A series of laboratory experiments have been conducted to verify this wash‐off model. It shows that the pollutant concentration and pollutant transport rate can be predicted well by the newly developed equations. It is found that the pollutant concentration monotonically decreases to zero as the accumulated pollutants are washed off, whereas the pollutant transport rate first increases to the maximum value and then decreases to zero. The maximum pollutant transport rate is found to increase with the decrease of the arrival time of the maximum value. The difference between the simplified exponential model and the amended wash‐off equation depends on the initial residual percentage (P_c), but the present equation generally provides a more accurate representation of the wash‐off process of dissolved pollutants.     

Mercury distribution in Douro estuary (Portugal)

Determinations of dissolved reactive and total dissolved mercury, particulate and sedimentary mercury, dissolved organic carbon (DOC), particulate organic carbon (POC) and suspended particulate matter (SPM) have been made in the estuary of river Douro, in northern Portugal. The estuary was stratified by salinity along most of its length, it had low concentrations of SPM, typically <20 mg dm(-3), and concentrations of DOC in the range <1.0-1.8 mg dm(-3). The surface waters had a maximum dissolved concentration of reactive mercury of about 10 ng dm(-3), whereas for the more saline bottom waters it was about 65 ng dm(-3). The surface waters had maximum concentrations of total suspended particulate mercury of approximately 7 microg g(-1) and the bottom waters were always <1 microg g(-1). Concentrations of mercury in sediments was low and in the range from 0.06 to 0.18 microg g(-1). The transport of mercury in surface waters was mainly associated with organic-rich particulate matter, while in bottom waters the dissolved phase transport of mercury is more important. Lower particulate organic matter, formation of chlorocomplexes in more saline waters and eventually the presence of colloids appear to explain the difference of mercury partitioning in Douro estuarine waters.     

Th:U disequilibrium as an indicator of sediment resuspension in Thermaikos Gulf, northwestern Aegean Sea

²³⁴Th:²³⁸U disequilibria have been used extensively as tracers of particle dynamics in marine environments. ²³⁴Th (t_1/2=24.1 days) can be used as “proxy” for particle reactive pollutants, due to their similar rapid rate of scavenging onto particles and subsequent removal from the water column, to the sediments. Radioactive disequilibrium can be exploited to determine the rates and time-scales of processes occurring over days to months; in this instance the residence times of dissolved and particulate species with the benthic nepheloid layer (BNL).Three sampling cruises were undertaken in Thermaikos Gulf (NW Aegean Sea) during contrasting periods, to examine the impact of natural and anthropogenic activity on sediment resuspension. September and October 2001 represented background and trawling periods, respectively; January 2002 represented a mixed period, of trawling and storms.Dissolved ²³⁴Th is scavenged actively at the BNL, in the presence of suspended particulate material (SPM), with a mean residence time of 16 days. There is a weak inverse correlation between dissolved ²³⁴Th residence time and SPM concentration in the BNL, with the shortest residence times occurring during October 2001. No relationship was observed between particulate ²³⁴Th activities and SPM concentrations, indicating that particles are rapidly removed from the system, either by sinking or advection. The mean particulate ²³⁴Th residence time is 5 days.     

Transfer and deposition of gold in the Congo watershed

Gold has been measured in water and suspended particulate matter samples coming from the Oubangui-Congo system. Gold anomalies up to 800 pico M/l were measured at two different locations. These are interpreted as the result of gold transport by dissolved organic complexes. Everywhere else the gold content is in the range of 10⁻¹¹M/l and gold is present as an aurous hydroxichloride complex.The knowledge of both discharge rates and gold content allows a quantification of the gold input into the Atlantic ocean. Respective values for dissolved and particulate gold input are equal to 2.86 t/a and 2.95 t/a. Both chemical denudation and physical weathering rates were computed from this new set of data.     

UV spectrometry for measuring particulate organic matter in natural water

Ultraviolet (UV) spectra were measured to characterize the dissolved and particulate organic matter in a bog and to investigate the seasonal fluctuation of this organic matter. The optical density spectra in the UV region of dissolved organic matter (DOM) were proportional to ^–4, where is the wavelength of incident light. There was also small absorption on the ^–4 spectra. The optical density at a wavelength of 280 nm was proportional to the concentration of dissolved organic carbon (DOC). The spectra and the dependency of optical density on DOC did not vary throughout the investigation period. The UV spectra of acid extractions of particulate organic matter (POM) showed two absorption peaks at the wavelengths of 220 nm and 335 nm. These peaks are well represented by the sum of two Lorentz functions. The ratio of the absorbances,A ₂₈₀/A ₃₃₅, was dependent on the nitrogen/carbon ratio of POM and the chlorophyll fraction in particulate organic carbon (POC), and not dependent on POC itself. The dependency of POC absorption at 280 nm varied with this ratio which fluctuated seasonally.     

Determination of Partition Coefficients for Selected PAHs between Water and Dissolved Organic Matter

The fate and transport of highly hydrophobic chemicals are affected by the partitioning between water and dissolved organic carbon. Large variation in the partition coefficient (K_DOCw) is often found, due to the selection of model organic matter or potential experimental artifacts. To investigate the roles of the type of organic matter on the partitioning of highly hydrophobic compounds, the partition coefficients of eight selected polycyclic aromatic hydrocarbons (PAHs), with 3–6 aromatic rings, were determined using a passive dosing/extraction method between water and model dissolved organic matter (humic acid, fulvic acid, sodium dodecyl sulfate micelle (SDS), and 2‐hydroxypropyl‐β‐cyclodextrin). Although the K_DOCw values for 3–4 ring PAHs in this study were close to those reported in the literature, experimental K_DOCw values between Aldrich humic acid (AHA) and water were higher than values reported in the literature for 5–6 ring PAHs. The K_DOCw values were highest for AHA, followed by SDS and Suwannee river fulvic acid (SFA). The slopes of the linear regression between log K_DOCw and log K_ow were 1.23 (± 0.13), 0.82 (± 0.09), and 0.59 (± 0.13) for AHA, SDS, and SFA, respectively. The differences in the K_DOCw values between AHA and the other organic matter (SDS, SFA, and CD) increased with increasing hydrophobicity of the PAHs, showing that the sorption of highly hydrophobic chemicals to the humic acid fraction may be important in the presence of mixed organic matter.     

A critical zone observatory dedicated to suspended sediment transport: The meso-scale Galabre catchment (southern French Alps)

The 20 km² Galabre catchment belongs to the French network of critical zone observatories (OZCAR; Gaillardet et al., Vadose Zone Journal, 2018, 17(1), 1–24). It is representative of the sedimentary lithology and meteorological forcing found in Mediterranean and mountainous areas. Due to the presence of highly erodible and sloping badlands on various lithologies, the site was instrumented in 2007 to understand the dynamics of suspended sediments (SS) in such areas. Two meteorological stations including measurements of air temperature, wind speed and direction, air moisture, rainfall intensity, raindrop size and velocity distribution were installed both in the upper and lower part of the catchment. At the catchment outlet, a gauging station records the water level, temperature and turbidity (10 min time-step). Stream water samples are collected automatically to estimate SS concentration-turbidity relationships, allowing quantification of SS fluxes with known uncertainty. The sediment samples are further characterized by measuring their particle size distributions and by applying a low-cost sediment fingerprinting approach using spectrocolorimetric tracers. Thus, the contributions of badlands located on different lithologies to total SS flux are quantified at a high temporal resolution, providing the opportunity to better analyse the links between meteorological forcing variability and watershed hydrosedimentary response. The set of measurements was extended to the dissolved phase in 2017. Both stream water electrical conductivity and major ion concentrations are measured each week and every 3 h during storm events. This extension of measurements to the dissolved phase will allow progress in understanding both the origin of the water during the events and the partitioning between particulate and dissolved fluxes of solutes in the critical zone. All data sets are available at https://doi.osug.fr/public/DRAIXBLEONE_GAL/index.html .     

Seasonal variation of polychlorinated biphenyl concentrations in the southern part of the Baltic Sea

The impact of seasonal fluctuations in forcing factors such as atmospheric concentration, temperature, and biological productivity on the concentration of polychlorinated biphenyls (PCBs) in the surface water of the southern part of the Baltic Sea was investigated. Water samples were collected on eight cruises over 2 years. A clear seasonal variability in dissolved PCB concentrations was observed with higher levels in summer than in winter and spring. This was attributed to changes in atmospheric concentrations and water temperature, based on measurements showing the PCB levels in the atmosphere and surface water to be close to a partitioning equilibrium. Concentrations in the suspended particulate material (SPM) fraction were also variable, and when the quotient of the organic carbon normalised concentration in SPM and the dissolved concentration was calculated (i.e., the bioaccumulation factor (BAF)), a seasonal pattern was observed which was consistent with kinetic limitations on partitioning into particles caused by plankton growth. However, seasonal variability in the partitioning properties of the SPM may also contribute to this variability.     

Enrichment and partitioning of polycyclic aromatic hydrocarbons in the sea surface microlayer and subsurface water along the coast of Xiamen Island,China

Sea microlayer (SML) and subsurface water (SSW) samples were collected around Xiamen Island to study the enrichment and partitioning of polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations ranged from 93.43 to 411.05 ng L⁻¹ in the SML and 49.29–279.42 ng L⁻¹ in the SSW. Compared with the results of previous studies before pollution control measurements, PAHs levels decreased significantly. The enrichment factors (EFs) of dissolved and particulate PAHs varied from 0.68 to 2.71 and 0.43–3.56. EFs showed the consistent enrichment trends with sites and exhibited different enrichment characteristics between 2 and 3 ring PAHs and 4 ring PAHs. Furthermore, the much higher concentrations of BaP (strong carcinogenicity) were accompanied by higher EFs in the SML samples from the Western Xiamen Harbour, which together indicated the risk of impacts to the fish eggs that usually float on the SML water after exposure to oil spills and combustion, contributed directly by the port and shipping activities.     

夏季东太湖光合有效辐射衰减特征及其对沉水植物恢复的指示

水下光照分布是影响水生态系统的重要因素,研究光合有效辐射衰减特征对于沉水植物恢复具有一定的指导意义.根据沉水植物生物量资料,将东太湖划分为沉水植物茂盛区、沉水植物稀疏区和无植物区3种区域.基于2019年夏季原位水下光场资料,探讨了东太湖光衰减特性和光照衰减因子的空间差异以及不同区域内的主导衰减因子,分析了东太湖的稳态阶段和富营养化水平,并阐述了真光层深度与透明度的关系,以期为东太湖沉水植物恢复和保护提供相关资料.结果表明:东太湖不同区域光衰减特性差异显著,光合有效辐射衰减系数(k d(PAR))在0.73~11.80 m^-1之间变化,真光层深度范围为0.39~6.31 m.不同区域的无机悬浮物和有机悬浮物浓度存在显著性差异,稀疏区叶绿素a浓度显著高于茂盛区,而与无植物区没有显著差异,有色可溶性有机物(CDOM)吸收系数在3种区域无显著性差异.k d(PAR)与无机、有机悬浮物的线性拟合效果较好,而与叶绿素a、CDOM拟合较差.水体吸收和散射作用是茂盛区光衰减的主要原因,无植物区域主导衰减因子仅有无机悬浮物,稀疏区由叶绿素a和无机悬浮物共同主导,是生态修复需要重点关注的区域,有机悬浮物和CDOM对东太湖光照衰减没有太大影响.东太湖目前正处于从草型稳态向藻型稳态过渡的阶段,整个湖泊属于富营养水平,真光层深度大约为透明度的2.7倍.     

Some aspects of vanadium and chromium chemistry in the English Channel

Dissolved and particulate vanadium and chromium concentrations along a transect between Cherbourg and the Isle of Wight were investigated in the English Channel. Seawater samples were collected at two different depths (surface and bottom) at five sampling stations during five cruises carried out between September 1994 and September 1995. Calculated mass flows through this Channel section were 7600 T yr⁻¹ for vanadium (about 66% was in the dissolved phase) and 1650 T yr⁻¹ for chromium (about 50% was in the dissolved phase). Dissolved chromium concentrations do not vary significantly along the transect. Seasonal variations in chromium distribution linked to biotic parameters were noted during the September 1994 cruise, when a significant relationship between particulate chromium and algal organic carbon was found. In addition, dissolved Cr (III) and Cr (VI) were well correlated with both algal and terrestrial organic matter. In the May cruise, during phytoplanktonic decay, particulate chromium was correlated with the detritic and bacterial organic fractions. These observations suggest interactions between chromium and biotic material. During the winter period, no relationship between chromium and POC was found. Dissolved and particulate vanadium concentrations varied, respectively, between 15 and 28 nmol l⁻¹ and 2–32 nmol l⁻¹. Values of dissolved vanadium showed depletion in the Channel with respect to oceanic waters. This loss in dissolved vanadium was higher near the English coast, but was compensated for by the increase in the particulate vanadium. There was no clear relationship between dissolved vanadium and algal organic carbon and it is inferred that the vanadium transfer cannot be explained by trapping with biotic material. On the other hand, the dissolved vanadium depletion could be attributed to the presence of ferric oxyhydroxide phases in particles, which have strong adsorbing properties for a range of dissolved metal ions.     

Effects of In Situ Remediation Using Oxidants or Surfactants on Subsurface Organic Matter and Sorption of Trichloroethene

In situ remediation technologies have the potential to alter subsurface properties such as natural organic matter (NOM) content or character, which could affect the organic carbon‐water partitioning behavior of chlorinated organic solvents, including dense nonaqueous phase liquids (DNAPLs). Laboratory experiments were completed to determine the nature and extent of changes in the partitioning behavior of trichloroethene (TCE) caused by in situ chemical oxidation or in situ surfactant flushing. Sandy porous media were obtained from the subsurface at a site in Orlando, Florida. Experiments were run using soil slurries in zero‐headspace reactors (ZHRs) following a factorial design to study the effects of porous media properties (sand vs. loamy sand with different total organic carbon [TOC] contents), TCE concentration (DNAPL presence or absence), and remediation agent type (potassium permanganate vs. activated sodium persulfate, Dowfax 8390 vs. Tween 80). Results revealed that the fraction of organic carbon (f_oc) of porous media after treatment by oxidants or surfactants was higher or lower relative to that in the untreated media controls. Isotherm experiments were run using the treated and control media to measure the distribution coefficient (K_d) of TCE. Organic carbon‐water partitioning coefficient values (K_oc) calculated from the experimental data revealed that K_oc values for TCE in the porous media were altered via treatment using oxidants and surfactants. This alteration can affect the validity of estimates of contaminant mass remaining after remediation. Thus, potential changes in partitioning behavior should be considered to help avoid decision errors when judging the effectiveness of an in situ remediation technology.     

Evaluation of Monod kinetic parameters in the subsurface using moment analysis: Theory and numerical testing

The spatial moments of a contaminant plume undergoing bio-attenuation are coupled to the moments of microbial populations effecting that attenuation. In this paper, a scalable inverse method is developed for estimating field-scale Monod parameters such as the maximum microbial growth rate (μ^max), the contaminant half saturation coefficient (K_s), and the contaminant yield coefficient (Y_s). The method uses spatial moments that characterize the distribution of dissolved contaminant and active microbial biomass in the aquifer. A finite element model is used to generate hypothetical field-scale data to test the method under both homogeneous and heterogeneous aquifer conditions. Two general cases are examined. In the first, Monod parameters are estimated where it is assumed a microbial population comprised of a single bacterial species is attenuating one contaminant (e.g., an electron donor and an electron acceptor). In a second case, contaminant attenuation is attributed to a microbial consortium comprised of two microbial species, and Monod parameters for both species are estimated. Results indicate the inverse method is only slightly sensitive to aquifer heterogeneity and that estimation errors decrease as the sampling time interval decreases with respect to the groundwater travel time between sample locations. Optimum conditions for applying the scalable inverse method in both space and time are investigated under both homogeneous and heterogeneous aquifer conditions.     

226Ra,210Pb and210Po in the Red Sea

Profiles of²²⁶Ra and dissolved²¹⁰Pb have been measured at several stations in the Red Sea. At one station in the central Red Sea an expanded profile was measured including²²⁶Ra and dissolved and particulate²¹⁰Pb and²¹⁰Po. These profiles show several distinct features: (1)²²⁶Ra displays a mid-depth maximum of about 13 dpm/100 kg at about 500 m; (2) dissolved²¹⁰Pb concentrations are uniformly low at about 2 dpm/100 kg with little lateral or vertical variation; (3) the surface-water²¹⁰Pb excess which is commonly observed in low-latitude open ocean regions is entirely lacking; (4)²¹⁰Pb and²¹⁰Po activities are essentially identical to each other in both particulate and dissolved phases although²¹⁰Po activities appear somewhat lower; (5) about 20% of the²¹⁰Pb and²¹⁰Po in the water column residues on particulate matter.Assuming the atmospheric²¹⁰Pb flux to be in the dissolved form and at the lower level of the normal range i.e. 0.5 dpm/cm² yr, the residence time of the dissolved Pb is about 1.5 years. However, if the same atmospheric flux is entirely in particulate form, then the residence time of the dissolved Pb is about 5 years. The residence time of Pb in the particulate phase is less than 0.4 years if all the Pb is removed only by sinking particles.