Partitioning of chloroaromatic compounds between the aqueous phase and dissolved and particulate soil organic matter at chlorophenol contaminated sites

The retention and mobility of hydrophobic organic contaminants (HOCs) in soil is mainly determined by hydrophobic partitioning to dissolved and particulate organic matter (DOM and POM, respectively). The aqueous phase, DOM, and POM fractions were extracted and separated from soils at three sites contaminated with technical chlorophenol formulations. Concentrations of chlorophenols (CP), polychlorinated phenoxyphenols (PCPP), polychlorinated diphenyl ethers (PCDE) and polychlorinated dibenzo-p-dioxins and furans (PCDD/F) were determined. The partitioning to POM, in relation to DOM, increased in all three soils with increasing hydrophobicity in the order CP < PCPP ~ PCDE ~ PCDF < PCDD. Differences in partitioning to DOM (logK(DOC)) and POM (logK(POC)) could not be explained by differences in gross organic C chemistry. Black carbon did not contribute significantly to the sorption of PCDDs, whereas >70% wood fibre in one soil resulted in a decrease of logK(POC) of 0.5 units for CPs and PCDDs. We conclude that logK(OC) for both DOM and POM need to be explicitly determined when the retention and mobility of HOCs is described and modelled in soils.     

Evaluating the impacts of some environmentally relevant factors on the availability of bisphenol A with negligible-depletion SPME

The effect of some environmentally relevant factors including salinity, pH, and humic acids on the availability of bisphenol A (BPA) was evaluated by using the negligible-depletion solid-phase microextraction (nd-SPME) biomimetic method. With the variation of salinity (0–500 mM NaCl) and pH (5.0–8.5) of aqueous solutions, the partition coefficients of BPA between the nd-SPME fiber and the aqueous solution varied in the range of log D = 3.55–3.86, which indicates that the salinity and pH can influence the availability of BPA. By using Acros humic acid as model dissolved organic matter (DOM), it was also demonstrated that the environmental factors such as salinity and pH could affect the partitioning of BPA between DOM and aqueous solutions. The determined partition coefficients of BPA between dissolved organic carbon (DOC) and aqueous solutions were in the range of log D_DOC = 4.03–5.60 for Acros humic acid solutions with 1–50 mg l⁻¹ DOC. The influence of salinity and pH on log D_DOC was more significant at low concentration (0–5 mg l⁻¹) of DOC.     

Effect of catchment land use and soil type on the concentration,quality, and bacterial degradation of riverine dissolved organic matter

We studied the effects of catchment characteristics (soil type and land use) on the concentration and quality of dissolved organic matter (DOM) in river water and on the bacterial degradation of terrestrial DOM. The share of organic soil was the strongest predictor of high concentrations of dissolved organic carbon, nitrogen, and phosphorus (DOC, DON, and DOP, respectively), and was linked to DOM quality. Soil type was more important than land use in determining the concentration and quality of riverine DOM. On average, 5–9 % of the DOC and 45 % of the DON were degraded by the bacterial communities within 2–3 months. Simultaneously, the proportion of humic-like compounds in the DOM pool increased. Bioavailable DON accounted for approximately one-third of the total bioavailable dissolved nitrogen, and thus, terrestrial DON can markedly contribute to the coastal plankton dynamics and support the heterotrophic food web.     

Spatial distribution and mobility of organic carbon (POC and DOC) in a coastal Mediterranean environment (Saronikos Gulf, Greece) during 2007–2009 period

Particulate (POC) and dissolved organic carbon (DOC) is an important parameter for the pollution assessment of coastal marine systems, especially those affected by anthropogenic, domestic, and industrial activities. In the present paper, a similar marine system (Saronikos Gulf) located in the west-central Aegean Sea (eastern Mediterranean Sea) was examined, in terms of the temporal and spatial distribution of organic carbon (POC and DOC), with respect to marine sources and pathways. POC was maximum in winter in the Saronikos Gulf, due to the bloom of phytoplankton, whereas in the Elefsis Bay (located in the north side of the Saronikos Gulf) in summer, since phytoplankton grazes in the Bay in the end of summer (except for winter). Approximately 60 % of the bulk DOC of the water column was estimated as non-refractory (labile and semi-labile), due to the major anthropogenic, domestic, and industrial effects of the region and the shallow depths. The spatial distribution of POC and DOC mainly affects the northeastern section of the Gulf, since that region has been accepted major organic discharges for a long time period, in connection to the relatively long renewal times of its waters.     

Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements

The potential of effluent DOM to undergo microbial degradation was assessed in batch experiments. Effluent samples from Haifa wastewater treatment plant and Qishon reservoir (Greater Haifa wastewater reclamation complex, Israel) were incubated either with effluent or soil microorganisms for a period of 2-4 months and were characterized by dissolved organic carbon contents (DOC), UV(254) absorbance and by fluorescence excitation-emission matrices. Three main fluorescence peaks were identified that can be attributed to humic/fulvic components and "protein-like" structures. During biodegradation, specific fluorescences (F/DOC) of the three peaks were increased at various extents, suggesting selective degradation of non-fluorescing constituents. In some cases increase in the effluent fluorescence (F) was observed thus proposing (i) the formation of new fluorescing material associated with DOM biodegradation and/or (ii) degradation of certain organic components capable of quenching DOM fluorescence. Based on the ratio between fluorescence intensity and UV(254), different biodegradation dynamics for fluorescent DOM constituents as compared with other UV-absorbing molecules was delineated. Overall, about 50% of the total DOM was found to be readily degradable such that residual resistant DOC levels were between 8 and 10 mg l(-1). Enhanced levels of residual DOM in effluent-irrigated soils may contribute to the DOM pool capable of carrying pollutants to groundwater.     

Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.     

The size distribution of organic carbon in headwater streams in the Amazon basin

Despite the strong representativeness of streams in the Amazon basin, their role in the accumulation of coarse particulate organic carbon (CPOC), fine particulate organic carbon (FPOC), and dissolved organic carbon (DOC) in transport, an important energy source in these environments, is poorly known. It is known that the arboreal vegetation in the Amazon basin is influenced by soil fertility and rainfall gradients, but would these gradients promote local differences in organic matter in headwater streams? To answer this question, 14 low-order streams were selected within these gradients along the Amazon basin, with extensions that varied between 4 and 8 km. The efficiency of the transformation of particulate into dissolved carbon fractions was assessed for each stream. The mean monthly benthic organic matter storage ranged between 1.58 and 9.40 t ha^?1 month^?1. In all locations, CPOC was the most abundant fraction in biomass, followed by FPOC and DOC. Rainfall and soil fertility influenced the distribution of the C fraction (p?=?0.01), showing differentiated particulate organic carbon (POC) storage and DOC transportation along the basin. Furthermore, the results revealed that carbon quantification at the basin level could be underestimated, ultimately influencing the global carbon calculations for the region. This is especially due to the fact that the majority of studies consider only fine particulate organic matter and dissolved organic matter, which represent less than 50 % of the stored and transported carbon in streambeds.     

Partitioning and source diagnostics of polycyclic aromatic hydrocarbons in rivers in Tianjin, China

Water, suspended particulate matter (SPM), and sediment samples were collected from ten rivers in Tianjin and analyzed for 16 polycyclic aromatic hydrocarbons (PAHs), dissolved organic carbon (DOC), particulate organic carbon (POC) in SPM and total organic carbon (TOC) in sediment. The behavior and fate of PAHs influenced by these parameters were examined. Generally, organic carbon was the primary factor controlling the behavior of the 16 PAH species. Partitioning of PAHs between SPM and water phase was studied, and K(OC) for some PAH species were found to be significantly higher than the predicted values. The source of PAHs contamination was diagnosed by using PAH isomer ratios. Coal combustion was identified to be a long-term and prevailing contamination source for sediment, while sewage/wastewater source could reasonably explain a short-term PAHs contamination of SPM.     

Effect of dissolved organic carbon on the environmental distribution of nonpolar organic compounds

The effect of dissolved organic carbon on the process of pollutant sorption to aquatic sediments was studied using sediments from the Boonton Reservoir/Rockaway River system in northern New Jersey. Addition of DOC to the aqueous phase reduced the sorption of DDT to sediments, but had no effect on the sorption of Lindane. The effect of the DOC is to increase the amount of DDT in the soluble phase and enable transport of the compound throughout an aquatic system. The apparent influence of DOC on the equilibrium distribution of organic compounds is illustrated by modifying an existing environmental model.     

Characteristics of mercury speciation in Minnesota rivers and streams

Patterns of mercury (Hg) speciation were examined in four Minnesota streams ranging from the main-stem Mississippi River to small tributaries in the basin. Filtered phase concentrations of methylmercury (MeHg), inorganic Hg (IHg), and dissolved organic carbon (DOC) were higher in all streams during a major summertime runoff event, and DOC was enriched with MeHg but not with IHg. Particulate-phase MeHg and IHg concentrations generally increased with total suspended solids (TSS) concentrations but the event data did not diverge greatly from the non-event data, suggesting that sources of suspended sediments in these streams did not vary significantly between event and non-event samplings. The dissolved fractions (filtered concentration/unfiltered concentration) of both MeHg and IHg increased with increasing DOC concentrations, but varied inversely with TSS concentrations. While MeHg typically constitutes only a minor portion of the total Hg (THg) in these streams, this contribution is not constant and can vary greatly over time in response to watershed inputs.     

Differentiating with fluorescence spectroscopy the sources of dissolved organic matter in soils subjected to drying

The relative fluorescence, normalised on dissolved organic carbon (DOC), and a humification index, based on the location of the fluorescence emission spectra, were used to investigate the possible sources of the increase in dissolved organic matter (DOM) when a soil is dried. From these 2 parameters it could be seen that air drying resulted in a minor increase of more humified material in DOM while the effect of oven drying was mainly due to cell lysis.     

Influence of temperature and origin of dissolved organic matter on the partitioning behavior of polycyclic aromatic hydrocarbons

Background, aim, and scope  

The behavior of polycyclic aromatic hydrocarbons (PAHs) is affected by dissolved organic matter (DOM) present in pore water of soils and sediments. Since partitioning to DOM reduces the bioavailable or freely dissolved PAH concentration in pore water, it is important to assess the effect of environmental variables on the magnitude of dissolved organic matter to water partition coefficients (K _DOC). The objective of this study was to apply passive samplers to measure freely dissolved PAHs allowing depletion from the aqueous phase. The method was applied to determine K _DOC at different temperatures for a selection of PAHs with natural DOM of very different origin.     

Quantity and spectroscopic properties of soil dissolved organic matter (DOM) as a function of soil sample treatments: air-drying and pre-incubation

The dissolved organic matter (DOM) in soils is essentially defined by the way in which it is obtained. Therefore, we need to understand as to how pre-treatment of a soil will affect the characteristics of DOM, since this fraction may be strongly influenced by a soil's water content. The effect of two different pre-treatments on DOM from the A-horizons of a large variety of ecosystems and regions were compared. In both cases the soils were allowed to air-dry. In one case the air-dried soil was directly extracted (AD), while in the other case it was preincubated for 1 week at 50% of its water holding capacity (INCU). AD is simpler, but INCU brings the soil, and especially its microbial population, back to a standardised state, which is more representative of the usual state in the field. Both methods are used whenever an adjustment of the soil water content is essential to compare different regions or to eliminate short term weather effects. A significant regression indicated that the dissolved organic carbon (DOC) extracted from INCU samples was only 20% of AD DOC. Both the absorptivity (UV absorption divided by DOC) of 86% of the samples, and a fluorescence emission spectrum based Humification Index in all cases increased as a result of preincubation. This would indicate that labile compounds released during drying were metabolised during the incubation. However, the magnitude of this increase varied, and no correlation with soil organic and microbial carbon, pH, or texture could be detected. The results show that DOM extracted from AD and INCU soils is not comparable and that the differences are mainly due to the impact of air-drying on the microbial activity.     

Seasonal and air mass trajectory effects on dissolved organic matter of bulk deposition at a coastal town in south-western Europe

Rainwater contains a complex mixture of organic compounds which may influence climate, terrestrial and maritime ecosystems and thus human health. In this work, the characteristics of DOM of bulk deposition at a coastal town on the southwest of Europe were assessed by UV–visible and three-dimensional excitation–emission matrix fluorescence spectroscopies and by dissolved organic carbon (DOC) content. The seasonal and air mass trajectory effects on dissolved organic matter (DOM) of bulk deposition were evaluated. The absorbance at 250 nm (UV_250nm) and integrated fluorescence showed to be positively correlated with each other, and they were also positively correlated to the DOC in bulk deposition, which suggest that a constant fraction of DOM is likely to fluoresce. There was more chromophoric dissolved organic matter (CDOM) present in summer and autumn seasons than in winter and spring. Bulk deposition associated with terrestrial air masses contained a higher CDOM content than bulk deposition related to marine air masses, thus highlighting the contribution of terrestrial/anthropogenic sources.     

Leaching characteristics of PCDDs/DFs and dioxin-like PCBs from landfills containing municipal solid waste and incineration residues

To investigate the leaching characteristic of persistent organic pollutants (POPs), such as non-ortho and mono-ortho substituted chlorobiphebyls (dioxin-like PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), in leachate from municipal solid waste (MSW) landfill sites containing incineration residues, raw leachate samples were collected twice from 12 selected MSW landfill sites. The samples were divided into their liquid and solid phases using GF/B (pore size 1.0 microm), and the concentrations of POPs then determined. The concentrations of PCDDs/DFs ranged from 0.65 to 5.88 pg-TEQ/l (average 2.86 pg-TEQ/l), and those of dioxin-like PCBs from 0.05 to 0.32 pg-TEQ/l (average 0.18 pg-TEQ/l). The major congeners of leached PCDDs/DFs and dioxin-like PCBs in liquid and solid phases were OCDD (about 60%), 2,3',4,4',5-PeCBs (about 30%), and 2,3,4,4',5-PeCBs (about 54%). The relationship between landfill age and the leaching concentration of PCDDs/DFs, and effects of dissolved organic carbon (DOC) on the leaching of PCDDs/DFs are also discussed. Finally, a leaching prediction model of PCDDs/DFs from MSW landfills has been suggested using parameters, such as hydrophobic neutral organic carbons, total dissolved solid, and the ratio of non-biodegradable wastes in landfill sites.     

Mobility of chloroaromatic compounds in soil: case studies of Swedish chlorophenol-contaminated sawmill sites

This paper summarizes recent studies on the environmental fate of chloroaromatic compounds in chlorophenol (CP)-contaminated soil and groundwater at Swedish sawmill sites. Relative proportions of CPs, polychlorinated phenoxy phenols (PCPPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) were determined in preservatives, particulate organic matter (POM), dissolved organic matter (DOM), groundwater, and particles filtered from groundwater. All compound classes were found in the different compartments. The fraction of PCPPs, PCDEs, PCDDs, and PCDFs had increased in the soil samples relative to the proportions in the preservatives. This increase showed correlation with the hydrophobicity, that is, PCDDs had the largest increase. Similar correlation was found between hydrophobicity and the importance of partitioning to POM over DOM. The more water soluble compound group, CP, was found equally distributed between POM and DOM. For PCPPs, PCDEs, PCDDs, and PCDFs, the relative partitioning to POM increased with increased hydrophobicity. Despite the relative partitioning towards POM, compared with DOM, cotransport with DOM and suspended colloidal fractions was found to substantially increase the transport of these compounds in the groundwater samples.     

Improvement of DOC removal by multi-stage AOP-biological treatment

The single and multi-stages advanced oxidation process (AOP)-biological treatments were evaluated to apply for drinking water treatment, especially for the water containing less susceptible dissolved organic carbon (DOC) to ozone, comparing with the ozonation-biological treatment. Minaga reservoir water and the secondary effluent from a Municipal wastewater treatment plant were used as dissolved organic matter (DOM) solutions. DOC removals after 60 min AOP-biological treatment were 62% and 41% in the Minaga reservoir water and the secondary effluent, respectively, whereas those in the ozonation-biological treatment only 40% and 15% of DOC were removed, respectively. The result indicated that the single-stage AOP-biological treatment could improve DOC removal in comparison with the single-stage ozonation-biological treatment. This is because the AOP mineralized both biodegradable dissolved organic carbon (BDOC) produced in the early stage of oxidation and non-biodegradable dissolved organic carbon (NBDOC), whereas only BDOC was mineralized by further ozonation and NBDOC was not oxidized in the ozonation-biological treatment. The multi-stage treatment could not improve DOC removal in comparison with the single-stage treatment in the ozonation-biological treatment for the secondary effluent containing less susceptible DOC to ozone. However, the multi-stage AOP-biological treatment significantly reduced DOC and achieved 71% of DOC removal by 4 times repetition of 15 min oxidation, whereas DOC removal was 41% in the single-stage AOP-biological treatment for the same oxidation time. The improvement of DOC removal by the multi-stage AOP-biological treatment was due to BDOC removal as a radical scavenger by subsequent biological treatment in the early stage of oxidation and direct mineralization in the latter stage of oxidation.     

Influence of soil conditions on dissolved organic matter leached from forest and wetland soils: a controlled growth chamber study

This study investigated the effects of various soil conditions, including drying-rewetting, nitrogen deposition, and temperature rise, on the quantities and the composition of dissolved organic matter leached from forest and wetland soils. A set of forest and wetland soils with and without the nitrogen deposition were incubated in the growth chambers under three different temperatures. The moisture contents were kept constant, except for two-week drying intervals. Comparisons between the original and the treated samples revealed that drying-rewetting was a crucial environmental factor driving changes in the amount of dissolved organic carbon (DOC). The DOC was also notably increased by the nitrogen deposition to the dry forest soil and was affected by the temperature of the dry wetland soil. A parallel factor (PARAFAC) analysis identified three sub-fractions of the fluorescent dissolved organic matter (FDOM) from the fluorescence excitation–emission matrices (EEMs), and their compositions depended on drying-rewetting. The data as a whole, including the DOC and PARAFAC components and other optical indices, were possibly explained by the two main variables, which were closely related with the PARAFAC components and DOC based on principal component analysis (PCA). Our results suggested that the DOC and PARAFAC component information could provide a comprehensive interpretation of the changes in the soil-leached DOM in response to the different environmental conditions.     

Aging and temperature effects on DOC and elemental release from a metal contaminated soil

The combined effect of time and temperature on elemental release and speciation from a metal contaminated soil (Master Old Site, MOS) was investigated. The soil was equilibrated at 10, 28, 45, 70 and 90 degrees C for 2 days, 2 weeks, and 2 months in the laboratory. Dissolved organic carbon (DOC), total soluble elements (by ICP), and labile metals (by DPASV) were determined in the filtered (0.22 microm) supernatants. For the samples equilibrated at 90 degrees C, DOC fractions were size fractionated by filtration and centrifugation; a subsample was only centrifuged while another was also filtered through a 0.45 microm filter. Analyses of the supernatants (ICP, DPASV, DOC) were performed on all size fraction subsamples. Dissolved organic carbon (DOC) increased both with temperature and incubation time; however, metal behavior was not as uniform. In general, total soluble metal release (ICP) paralleled the behavior of DOC, increasing with both time and temperature, and confirming the importance of soil organic matter (SOM) in metal retention. Voltammetric analysis (dpasv) of Cu and Zn showed that very little of these metals remains labile in solution due, presumably, to complexation with dissolved organic matter. Labile concentrations of Cd, on the other hand, constituted a significant portion (50%) of total soluble Cd. Copper and Al increased in solution with time (up to 2 months) and temperature up to 70 degrees C; however, at 90 degrees C the soluble concentration declined sharply. The same behavior was observed after equilibration for longer periods of time (550 days) at lower temperatures (23 and 70 degrees C). While concentrations of labile Cu and total soluble Cu and Al increased in the unfiltered samples, the trend remained the same. DPASV analysis showing shifts in labile Cu complexes with temperature and time, together with the results from the unfiltered samples, lead to the hypothesis that Cu was complexing with large polymers that could form at the elevated temperature, and thus be removed from the analyzed solution. It is possible that Cu and Al released by SOM oxidation has re-sorbed or complexed to more recalcitrant organic matter or to mineral phases. Variations in the relative molecular size fractions present within the DOC pool produced by increased time and temperature may influence the element-DOC complexes present in solution and their behavior in soil environments.     

Water quality parameters controlling the photodegradation of two herbicides in surface waters of the Columbia Basin,Washington

The water quality parameters nitrate-nitrogen, dissolved organic carbon, and suspended solids were correlated with photodegradation rates of the herbicides atrazine and 2,4-D in samples collected from four sites in the Columbia River Basin, Washington, USA. Surface water samples were collected in May, July, and October 2010 and analyzed for the water quality parameters. Photolysis rates for the two herbicides in the surface water samples were then evaluated under a xenon arc lamp. Photolysis rates of atrazine and 2,4-D were similar with rate constants averaging 0.025 h⁻¹ for atrazine and 0.039 h⁻¹ for 2,4-D. Based on multiple regression analysis, nitrate-nitrogen was the primary predictor of photolysis for both atrazine and 2,4-D, with dissolved organic carbon also a predictor for some sites. However, at sites where suspended solids concentrations were elevated, photolysis rates of the two herbicides were controlled by the suspended solids concentration. The results of this research provide a basis for evaluating and predicting herbicide photolysis rates in shallow surface waters.