Phosphorus Release and Equilibrium Dynamics of Canal Sediments within the Everglades Agricultural Area, Florida

High phosphorus (P) in surface drainage water from agricultural and urban runoff is the main cause of eutrophication within aquatic systems in South Florida, including the Everglades. While primary sources of P in drainage canals in the Everglades Agricultural Area (EAA) are from land use application of agricultural chemicals and oxidation of the organic soils, internal sources from canal sediments can also affect overall P status in the water column. In this paper, we evaluate P release and equilibrium dynamics from three conveyance canals within the EAA. Incubation and flux experiments were conducted on intact sediment cores collected from four locations within the Miami, West Palm Beach (WPB), and Ocean canal. After three continuous exchanges, Miami canal sediments reported the highest P release (66?±?37 mg m^?2) compared to WPB (13?±?10 mg m^?2) and Ocean (17?±?11 mg m^?2) canal over 84 days. Overall, the P flux from all three canal sediments was highest during the first exchange. Miami canal sediments showed the highest P flux (2.4?±?1.3 mg m^?2 day^?1) compared to WPB (0.83?±?0.39 mg m^?2?d^?1) and Ocean canal sediments (0.98?±?0.38 mg m^?2 day^?1). Low P release from WPB canal sediments despite having high TP content could be due to carbonate layers distributed throughout the sediment column inhibiting P release. Equilibrium P concentrations estimated from the sediment core experiment corresponded to 0.12?±?0.04 mg L^?1, 0.06?±?0.03 mg L^?1, and 0.08?±?0.03 mg L^?1 for Miami, WPB, and Ocean canal sediments, respectively, indicating Miami canal sediments behave as a source of P, while Ocean and WPB canal sediments are in equilibrium with the water column. Overall, the sediments showed a significant positive correlation between P release and total P (r?=?0.42), Fe_ox (r?=?0.65), and Al_ox (r?=?0.64) content of sediments. The contribution of P from the three main canals sediments within the EAA boundary corresponded to a very small portion of the total P load exiting the EAA. These estimates, however, only take into consideration diffusive fluxes from sediments and no other factors such as canal flow, bioturbation, resuspension, and anaerobic conditions.     

Seasonal delivery of organic matter and metals to farm canals: effect on sediment phosphorus storage capacity

Purpose

The Everglades Agricultural Area (EAA), USA, comprises nearly 280,000 ha of organic soil farmlands that are drained by a network of farm canals. During the wet summer season, the water-table in the farmlands is maintained by moving water from farm canals via low-fit, high-volume drainage pumps. The drainage pumping creates a hydraulic pressure gradient, which has the potential to deliver particulate and dissolved substrates from surrounding farmlands into farm canals. This study investigated the role that seasonal drainage plays on the fate and transport of farm canal water including nutrients and metals, plants, and sediments.

Materials and methods

Intact sediment cores were collected from eight farm canals during the months of November and June, sectioned into two depth intervals (0–2.5 and 2.5–5 cm), and tested for organic matter (OM), phosphorus (P), iron (Fe), and aluminum (Al). In addition, water from the canal (core-water) was also collected and tested for total P, total dissolved P, soluble reactive P, particulate P, dissolved organic carbon, and calcium (Ca). Oxalate extractable Fe, Al, and P were used to estimate sediment P storage capacity. In order to evaluate the seasonal variability in aquatic vegetation coverage in the farm canals, spatial assessment of coverage was conducted every 2 months over a 2-year period.

Results and discussion

Significant increases in Fe and Al concentrations were observed in the sediment in November compared with June, possibly derived from surrounding soils. The source of OM to the sediments was directly associated with aquatic plants, following a seasonal trend. Total P and Ca were significantly higher in the water during June compared with November. The seasonal trends in sediment and core-water concentrations can be explained by groundwater inputs, surface runoff, and plant coverage within farm canals. High concentrations of Fe and Al in the sediments did not reflect a high P storage capacity, due to the presence of high OM content and seasonal fluctuations in redox potential.

Conclusions

The discharge of groundwater from surrounding farmlands is seasonal and has the potential to deliver nutrients, OM, and metals into adjacent farm canals. During summer, primary productivity is at its peak, and this has a direct effect on the percent aquatic plant coverage, nutrient cycling, and P storage capacity within the farm canals. Within the EAA farm canals, the presence of Ca-carbonate may have a greater influence on P storage capacity of the sediments than Fe and Al.     

Ultra trace level mercury in the Everglades ecosystem,a multi-media canal pilot study

The Florida Everglades ecosystem is composed of the largest deposit (9600 km²) of near neutral peat in the world extending south of Lake Okeechobee to Florida Bay. The federal Central and South Florida Flood Control Project (C&SF) has sectioned the historic Everglades with a system of canals and levees to control water for urban and agricultural development, resulting in pronounced hydrologic modifications to the natural system. As a part of a comprehensive ecological risk assessment of mercury (Hg) contamination in the Everglades ecosystem, a pilot study of canals was initiated in September 1993 to determine the extent and magnitude of total (HgT) and methylmercury (MeHg) in water, sediment and fish. A probability-based random sampling grid was used to obtain consistent estimates of Hg contamination over this large geographic area. Two hundred canal sampling locations were selected as probability samples by associating grid points on the sampling frame with specific canal sections for independent sampling cycles. Of this number 50 locations were randomly selected for sampling in this pilot study. The selected canal points were sampled from north to south during a six day period. Cumulative distributions with 95% confidence intervals were calculated and used to determine a canal system median concentration for selected water, sediment and fish constituents. The percent exceedance of each median, by hydrologic subarea, was determined to demonstrate the existence and direction of spatial gradients in the system. North to south (high to low) gradients were apparent for total phosphorus (TP), sulfate (SO₄), dissolved organic carbon (DOC), conductance, HgT and MeHg in water. However, the gradients were reversed from south to north for HgT in sediments and fish (Gambusia sp). The greatest Hg concentrations inGambusia sp. occurred in the same canals where largemouth bass had previously been found to be most contaminated.     

Comparison of Two Digestion Methods for Determining Total Phosphorus in Farm Canal Water

Abstract

Rapid and accurate determination of low‐level (0.01 to 1.0 mg L^?1) phosphorus (P) concentrations in farm canal water is important in evaluating water quality in the Everglades Agricultural Area (EAA) canals in south Florida. Two U.S. Environmental Protection Agency methods, persulfate digestion (365.1) and Kjeldahl digestion with mercury oxide (365.4), were used to analyze total P (TP) and total dissolved P (TDP) in two sets of representative canal water samples collected at low‐flow conditions in 2003 and high‐flow conditions in 2004. Quality assurance samples (blanks, duplicates, and spikes) were included to evaluate differences between the two digestion methods. Precision analysis had a mean of less than 5% for both TP and TDP using both methods. The high coefficient of correlations (r>0.98) indicated that the two methods were significantly correlated in determining TP and TDP of the samples. Low detection limits (0.004 mg L^?1) were achieved by the persulfate method. This method offers many other advantages over the mercury digestion: it produces no toxic mercury waste, uses less time, and uses a lower temperature. High suspended solids in canal water samples were not proven to be a problem when using the persulfate digestion, though lower spike recoveries were observed than those when using the mercury digestion. We conclude that persulfate digestion is a more sensitive and environmentally responsible alternative to and is, as precise as, the mercury method for routine determination of TP and TDP in water samples. This information is useful to environmental laboratories in monitoring P concentrations in surface and groundwater.     

Influence of suspended particulates on phosphorus loading exported from farm drainage during a storm event in the Everglades Agricultural Area

Purpose

The purpose of this study was to evaluate the influence of suspended particulates on P loading captured during a single storm event. The Everglades Agricultural Area of Florida comprises 280,000 ha of organic soil farmland artificially drained by ditches, canals, and pumps. Phosphorus (P)-enriched suspended particulates in canals are susceptible to transport and can contribute significantly to the overall P loads in drainage water.

Materials and methods

A settling tank experiment was conducted to capture suspended particulates during tropical storm Isaac in 2012 from three farms approximately 2.4 to 3.6 km² in size. Farm canal discharge water was collected in a series of two 200-L settling tanks over a 7-day drainage period, during tropical storm Isaac. Water from the settling tanks was siphoned through Imhoff settling cones, where the suspended particulates were allowed to settle and collected for P fractionation analyses, and compared to intact sediment cores collected from the canals.

Results and discussion

The discharged suspended particulates contained higher organic matter content, total P, and labile P fractions compared to the drainage canal sediments. Based on the equilibrium P concentrations, drainage canal sediments behave as a source of P to the water column. A 7-day continuous drainage event exported 4.7 to 11.1 t of suspended solids per farm, corresponding to 32 to 63 kg of particulate P being lost to downstream ecosystems. Drainage associated to this single 7-day storm event exported up to 61 % of the total annual farm P load.

Conclusions

It is evident from this study that short-term, high-intensity storm events can skew annual P loads due to the export of significantly higher suspended particulate matter from farm canals. Exported particulates rich in P, if captured and replenished back on farmlands, would be a sustainable farming practice that can provide a supplemental source of nutrients.

     

Long-term dispersal of heavy metals in a catchment affected by historic lead and zinc mining

Purpose

The Matylda catchment, in southern Poland, was polluted by the discharge of mine waters from a lead and zinc mine that inundated parts of a valley floor and caused the accumulation of metal-polluted sediments. After a partial reclamation of the mine site in the early 1980s, polluted sediments continue to accumulate on downstream floodplains and in fishponds. The aim of this study was to reconstruct the changes in metal dispersal during 100?years of mining and during the 40-year post-mining period and to propose a strategy for pollution mitigation in the area.

Materials and methods

Analyses of Cu, Cd, Pb, Zn, Mn, Ca, Mg and Fe concentrations, speciation of heavy metals and mineralogical analyses were undertaken on overbank sediment cores and in stream sediments. Concentrations of the same elements and macro-ions soluble in stream waters were also determined.

Results and discussion

Concentrations of Zn, Cd and Pb in the sediment profiles vary between 40,000 and 55,000, 300 and 600 and 30,000 and 50,000?mg?kg^-1, respectively. Changes of metal concentrations and the stratigraphy of sediments from the floodplains, stream channels and fishponds suggest rapid changes of metal loads migrating downstream during both the mining and post-mining periods. Since the time of mine closure, fine-grained, mine-derived sediments (ca. 12?cm thick) have been the main source of pollution of post-mining sediments and surface waters. Closure of the mine was followed by a relatively short period of rapid redistribution of sediment-associated heavy metals in the stream channel. Since the 1980s, the floodplain and fishponds have received a constant supply of metals. It contrasts with the slow sediment accretion rate and a rapid decrease of metal concentrations in floodplain pools due to dilution by decomposed leaf litter. A fivefold increase of Cd content in waters over the 4.6?km reach of the Matylda stream indicates continuous leaching of this element from the contaminated valley floor.

Conclusions

Unsuccessful mine site rehabilitation is due to leaching of mine-originated sediments dispersed over the valley bottom. However, the rate of metal remobilization over the last 40?years is low because of the small thickness and widespread anoxic conditions that prevail within both recent and mine-originated sediments and the alkaline pH of stream water, which reduces metal mobility. Distribution of the contaminated layer over a large area of the valley bottom precludes cost-efficient catchment rehabilitation.     

Characterization and optimization of the preparation procedure for solution P-31 NMR analysis of organic phosphorus in sediments

Purpose

The single-step sodium hydroxide?Cethylenediaminetetraacetic acid (NaOH?CEDTA) extraction is currently the most common preparation technique for the measurement of organic phosphorus (P) composition in sediments using solution ³¹P nuclear magnetic resonance (NMR). In this study, detailed investigations were conducted to evaluate the performance of this technique, with an objective of finding an optimal procedure for the measurement of sediment organic P.

Materials and methods

A single-step extraction with NaOH?CEDTA was investigated on two types of sediment, i.e., Fe/Al-rich sediment and calcareous sediment. The influence of different sediment preparation methods, NaOH?CEDTA compositions, solid:solution ratios, extraction time, pre-concentration techniques, and NMR sample frozen storage time on P extraction and solution ³¹P NMR analysis were investigated.

Results and discussion

Both air- and freeze-drying increased organic P extraction for the calcareous sediment. An extraction time of 16?h was sufficient for quantitative recovery of extracted organic P for both Fe/Al-rich and calcareous sediments. The use of a 1:8 solid:solution ratio achieved stronger NMR signals and greater P diversity than the use of a 1:20 ratio. Extraction of the two sediments with 0.25 NaOH?C50?mM EDTA favored ³¹P NMR detection by reducing the relaxation times required and the risk of organic P degradation compared to the use of stronger NaOH?CEDTA solutions. Rotary evaporation was a better technique for pre-concentration of the NaOH?CEDTA extracts than freeze drying. The concentrated extracts could be preserved by freezing (?20?°C) for at least 2?months.

Conclusions

An optimized procedure was developed based on these investigations, including freeze-drying of fresh sediments, extraction with 0.25?M NaOH?C50?mM EDTA for 16?h using a solid:solution ratio of 1:8, pre-concentration of the extract to the level of ??10 times of its original concentration using rotary evaporation, and storage of the NMR sample at ?20?°C until ³¹P NMR analysis.     

Phosphorus losses from two representative small catchments in the Mediterranean part of Spain

Purpose

Information about phosphorus (P) losses from agricultural catchments in Mediterranean environments is scarce. In this work, P losses in overland flow from two representative small Mediterranean catchments, one dominated by Alfisols and the other by Vertisols, were studied.

Materials and methods

At the lowest level of each catchment, overland flow was measured and several runoff samples taken in each runoff event during two growing seasons (2001–2002 and 2002–2003). After centrifugation, total P in sediments and total and molybdate reactive P in supernatant were determined. Different chemical extraction methods were used to quantify the forms of P in soils and sediments.

Results and discussion

Total P losses in the studied catchments ranged between 0.5 and 3.2 kg ha^?1 year^?1, losses higher than 2 kg P ha^?1 being observed in one event. Phosphorus was mainly lost in the sediments, the ratio of total dissolved P to particulate P being higher in the Alfisol than in the Vertisol catchment. Phosphorus concentration in sediments from the Vertisol catchment was similar to that in the source soils, whereas sediments in the Alfisol catchment had 2.1 times more inorganic P and 9 times more organic P (OP) than the source soils. In the latter catchment, there was an enrichment in the more labile inorganic P forms in the sediments relative to the source soils, which corresponds to a relative enrichment in iron (Fe) oxides by a factor of 2.4. Alfisols had lower TP contents and exhibited lower erosion rates than Vertisols in the studied period but they posed a greater environmental risk than the latter soils because their sediments were richer in P and had a higher proportion of P in forms bound to the Fe oxides compared to the source soils—these P forms can be easily released with the onset of reducing conditions at the bottom of waterbodies.

Conclusions

A study of the P enrichment ratios and the dominant P forms in eroded sediments is therefore necessary to predict the impact of P losses from soils on the ecological quality of waterbodies.     

Quantification of seasonal sediment and phosphorus transport dynamics in an agricultural watershed using radiometric fingerprinting techniques

Purpose

Phosphorus (P) is a limiting nutrient for most US Midwestern aquatic systems and, therefore, increases of P, through point or non-point sources (NPS) of pollution such as agriculture, causes eutrophication. Identifying specific NPS contributions (e.g., upland vs. stream channels) for sediments and P is difficult due to the distributed nature of the pollution. Therefore, studies which link the spatial and temporal aspects of sediment and P transport in these systems can help better characterize the extent of NPS pollution.

Materials and methods

Our study used fingerprinting techniques to determine sources of sediments in an agricultural watershed (the North Fork of the Pheasant Branch watershed; 12.4 km² area) in Wisconsin, USA, during the spring, summer, and fall seasons of 2009. The primary sources considered were uplands (cultivated fields), stream bank, and streambed. The model used fallout radionuclides, ¹³⁷Cs, and ²¹⁰Pb_xs, along with total P to determine primary sediment sources. A shorter-lived fallout radioisotope, ⁷Be, was used to determine the sediment age and percent new sediments in streambed and suspended sediment samples (via the ⁷Be/²¹⁰Pb_xs ratio).

Results and discussion

Upland areas were the primary source of suspended sediments in the stream channels followed by stream banks. The sediment age and percent new sediment for the streambed and suspended sediments showed that the channel contained and transported newer (or more recently tagged with ⁷Be) sediments in the spring season (9–131 days sediment age), while relatively old sediments (165–318 days) were moving through the channel system during the fall season.

Conclusions

Upland areas are the major contributors to in-stream suspended sediments in this watershed. Sediment resuspension in stream channels could play an important role during the later part of the year. Best management practices should be targeted in the upland areas to reduce the export of sediments and sediment-bound P from agricultural watersheds.     

Annual dynamics of persistent organic pollutants in various aquatic matrices: a case study in the Morava River in Zlín district,Czech Republic

Purpose

A multi-compartment monitoring study was performed to characterize the effect of environmental variables, such as temperature and water flow as well as sediment characteristics, on the distribution and transport of persistent organic pollutants (POPs) in a dynamic river system during 1 year in an industrial region in central Europe.

Materials and methods

Waterborne polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed over a period of 1 year at five sampling sites in the Morava River in the Czech Republic. Contaminants were measured monthly in riverbed sediments, freshly deposited sediments, water samples and passive samplers.

Results and discussion

Sediments are the main carrier of POPs in the river. Distinguishable patterns of PAHs, OCPs and PCBs in sediment indicate that their origin is from distinct sources and different transport pathways. The PAHs were identified as the dominant contaminant group of compounds with a mean concentration in sediment of 5,900 μg kg^?1. Such concentrations are up to 10 times higher than in the Danube River, into which Morava drains. In contrast, mean concentrations of PCBs, hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane and its breakdown products (DDTs) and hexachlorobenzene (HCB) of 6.0, 0.4, 4.2 and 6.0 μg kg¹, respectively, are similar to those in the Danube. With some exceptions, no significant difference in composition of surficial riverbed sediments and those collected using sediment traps was observed. Despite the presence of potential local pollutant sources, the differences in contaminant concentrations between sites in the region were in most cases not significant. Variations in POP concentrations in sediments are mainly induced by high flow events, whereas seasonal variability was not observed.

Conclusions

The changes in contaminant concentrations in Morava River sediments are induced by episodic high flow events that cause erosion of contaminant-containing particles and their deposition at suitable downstream sites.     

Characterization of sediment contamination patterns by hydrophobic pesticides to preserve ecosystem functions of drainage lakes

Purpose

Many drainage basins are terminal recipients of hydrophobic contaminants such as pesticides. To minimize adverse effects of the contaminated sediments on wildlife, it is important to understand sediment contamination patterns. This study was conducted at the Salton Sea, which is a heavily polluted large lake in southern California, USA, with the purpose to identify areas with minimal contamination so as to support species conservation.

Materials and methods

We investigated the horizontal and vertical distribution of 14 organochlorine pesticides (OCPs) and 12 currently used pesticides (CUPs) in playas at locations near the drainage outfalls. The data were subjected to spatial analysis using Kriging interpolation and converted to contour maps. Statistical comparisons were made among different areas, between different sediment depths, and between air-exposed and submerged sediments.

Results and discussion

Various OCPs were found near two drainage inlets, with mean concentrations of 6?C30???g?kg^?1 in air-exposed sediments and 3?C18???g?kg^?1 in submerged sediments. Chlordane (detected frequency, DF?=?77?%) and DDT derivatives (DF?=?100?%) were among the most frequently detected OCP. Significantly higher concentrations were found in air-exposed sediments than in submerged sediments, and in subsurface sediments than in surface sediments (P?<?0.01), suggesting historical deposition and burial. Sediments at many locations exceeded the threshold levels for DDE. A total of seven CUPs were detected with the maximum ??CUPs concentration of up to 27???g?kg^?1. Bifenthrin was the dominant CUP contaminant, representing more than 60?% of ??CUPs for most samples with the highest concentration of 26???g?kg^?1.

Conclusions

Findings from this study provide a snapshot of the spatial distribution in both horizontal and vertical directions of hydrophobic pesticides in a drainage-dominated lake, and such information and the method of investigation may be used for identifying areas of minimal contamination as alternative habitats for this and other impacted lakes.     

The role of stromatolites in explaining patterns of carbon, nitrogen, phosphorus, and silicon in the Se?ovlje saltern evaporation ponds (northern Adriatic Sea)

Purpose

In summer 2007, biweekly benthic fluxes of the biogenic elements carbon (C), nitrogen (N), silicon (Si), and phosphorus (P) were studied in the Se?ovlje saltern (salt-making facility) in the northern Adriatic Sea, Slovenia in order to determine the impact of stromatolite (??petola??) on the geochemical properties of saltern sediments.

Materials and methods

The brine and pore waters were analyzed for salinity, NH ₄ ⁺ , NO ₃ ^? , PO ₄ ^3? , SiO ₄ ^4? , total dissolved nitrogen, total dissolved phosphorus, and fluorescent dissolved organic matter. The sediment was analyzed for organic carbon (OC), total nitrogen (TN), total and organic phosphorus (OP), and biogenic Si concentrations, as well as values of ?? ¹³C_OC and ?? ¹⁵N_TN.

Results and discussion

Nutrient concentrations in brine water increased along the salinity gradient due to different processes, such as the evaporative concentrations of seawater, bacterial activity, more pronounced transformation and degradation of organic matter, and regeneration of nutrients. The petola from the Se?ovlje saltern, which is predominately composed of cyanobacterial and diatom communities, develops during the early evaporation stage and survives during high salinity and halite crystallization. Nitrogen fixation and P removal were the principal biogeochemical processes controlling dissolved inorganic N and P concentrations. At higher salinities, N limitation was more important. Microbes decomposed at higher salinities, and the remineralized N and P nutrients were released from surface pore waters to the brine. OP remineralization was also an important process influencing the distribution of PO ₄ ^3? concentrations in pore waters deeper in the sediments. The increasing SiO ₄ ^4? concentrations with increasing salinity in the brine waters were due to dissolution of diatom frustules, while the decrease in pore water SiO ₄ ^4? was probably the consequence of microbial uptake.

Conclusions

This study provides a better understanding of nutrient cycling and the geochemical processes in the Se?ovlje saltern.     

Evolution and phosphorus fractionation in saline Spolic Technosols flooded with eutrophic water

Purpose

The aim of this study was to evaluate the behaviour of P in saline Spolic Technosols flooded with eutrophic water, with and without plant rhizosphere, in order to assess the role of these soils as sinks or sources of this nutrient.

Materials and methods

Samples were taken from basic (pH?~7.8), carbonated and acidic (pH?~6.2), de-carbonated soils of salt marshes polluted by mine wastes. Three treatments were assayed: pots with Sarcocornia fruticosa, pots with Phragmites australis and pots without plants (bare soil). The pots were flooded for 15?weeks with eutrophic water (PO ₄ ^3? ~6.92?mg?L^?1) and pH, Eh and water-soluble organic carbon and PO ₄ ^3? concentrations were monitored in the soil solution. A soil P fractionation was applied before and after the flooding period.

Results and discussion

The PO ₄ ^3? concentration in the soil solution decreased rapidly in both soils, with and without plant, being diminished by 80?C90?% after 3?h of flooding. The Fe/Mn/Al oxides and the Ca/Mg compounds played an important role in soil P retention. In pots with S. fruticosa, the reductive conditions due to flooding induced P release from metal oxides and P retention to Ca/Mg compounds. In turn, P. australis may have favoured the release of P from carbonates, which was transferred to Fe/Mn/Al compounds.

Conclusions

The retention of P by the soil was the main mechanism involved in the removal of PO ₄ ^3? from the eutrophic flooding water but to evaluate the capacity of these systems as long-term P sinks, the combined effect of metals, Ca/Mg compounds and specific plant species should be considered.     

Spatial distribution of soil nutrient at depth in black soil of Northeast China: a case study of soil available phosphorus and total phosphorus

Purpose

The spatial variability of soil available phosphorus (AP) and total phosphorus (TP) influences crop yield and the environment. The paper aims to identify the spatial heterogeneity of P (AP and TP) and clarify the main driving mechanisms in a Mollisol watershed of Northeast China.

Materials and methods

Both geostatistical and traditional analysis were used to describe the spatial distribution of P at different depths. P in cultivated fields on the upper slopes was compared with secondary forest areas on the lower slopes within the same watershed.

Results and discussion

The horizontal distribution of P was found to be primarily influenced by structural factors (58–95 %). TP was high at both the summit and the bottom of slopes at all depths, being especially high at the watershed outlet due to erosion on the back slope and deposition at the base. AP was higher on south-facing slopes than on north-facing slopes and typically decreased from the summit to the base of south-facing slopes at the 0–40-cm depths, mainly due to solar radiation, soil loss, and water loss. The vertical distribution of TP typically decreased with increasing depths in farmland but did not show systematic variation in the forest profiles. AP was lower in the middle of the 0–60-cm soil profiles in the farmland, reflecting the influence of fertilization, infiltration, and crop absorption. AP in the 30–60-cm and TP in the 20–60-cm layers were lower in farmland than in the secondary forest, and only 2 % of the area showed a risk of P loss through ground flow and infiltration in the 0–20-cm layer.

Conclusions

The horizontal distribution of P in the 0–60-cm layers was mainly influenced by soil and water loss, deposition, and hydrothermal dynamics, while the vertical distribution of P, especially AP, was more affected by fertilization, infiltration, organic matter, and crop absorption. Secondary forestland that had been converted from farmland was found to effectively hold P, especially in deep soil layers, as the loss of P dissolved in water is not a primary process.     

Degradation and sorption of commonly detected PPCPs in wetland sediments under aerobic and anaerobic conditions

Purpose

Wetlands are a popular tool to treat/polish wastewater by reducing nutrient loading into the environment. In addition to nutrients, organic contaminants, such as pharmaceuticals and personal care products (PPCPs), are commonly detected in treated wastewater. Treatment wetlands may reduce concentrations of PPCPs before the treated effluent enters rivers and streams. Oxygen status may greatly affect the attenuation of PPCPs in wetland sediments by influencing microbial makeup and activity. An understanding of the effect of redox conditions on the degradation of PPCPs and the factors influencing PPCP sorption to wetland sediments is needed to maximize PPCP removal in treatment wetlands.

Materials and methods

Three wetland sediments from the San Diego Creek and Newport Bay watershed in Southern California, USA, were incubated under aerobic and anaerobic conditions to assess the degradation of several regularly occurring PPCPs and their phase distribution as a function of time.

Results and discussion

Under aerobic conditions, ibuprofen, N,N-diethyl-meta-toluamide (DEET), and gemfibrozil generally had half-life values around 20?days, while the half-life of carbamazepine was substantially longer (between 165 and 264?days). The anaerobic half-lives of gemfibrozil and ibuprofen increased by factors of 11?C34 and carbamazepine increased by factors of 1.5?C2.5. There was no detectable anaerobic degradation of DEET. The apparent phase distribution coefficient increased over time for DEET, carbamazepine and gemfibrozil, indicating that sorption of PPCPs to wetland sediments may be more limited than that predicted using equilibrium sorption coefficient values.

Conclusions

Knowledge of the capacity of wetland sediments for degrading and sorbing PPCPs is vital to the design of treatment wetlands. Degradation of the selected PPCPs was enhanced under aerobic conditions as compared to anaerobic conditions. Sorption to sediments increased with contact time, indicating that longer hydraulic retention will increase wetland capabilities for removing PPCPs.     

Lead mobilisation in the hyporheic zone and river bank sediments of a contaminated stream: contribution to diffuse pollution

Purpose

Past metal mining has left a legacy of highly contaminated sediments representing a significant diffuse source of contamination to water bodies in the UK and worldwide. This paper presents the results of an integrated approach used to define the role of sediments in contributing to the dissolved lead (Pb) loading to surface water in a mining-impacted catchment.

Materials and methods

The Rookhope Burn catchment, northern England, UK is affected by historical mining and processing of lead ore. Quantitative geochemical loading determinations, measurements of interstitial water chemistry from the stream hyporheic zone and inundation tests of bank sediments were carried out.

Results and discussion

High concentrations of Pb in the sediments from the catchment, identified from the British Geological Survey Geochemical Baseline Survey of the Environment (GBASE) data, demonstrate both the impact of mineralisation and widespread historical mining. The results from stream water show that the stream Pb load increased in the lower part of the catchment, without any apparent or significant contribution of point sources of Pb to the stream. Relative to surface water, the interstitial water of the hyporheic zone contained high concentrations of dissolved Pb in the lower reaches of the Rookhope Burn catchment, downstream of a former mine washing plant. Concentrations of 56???g?l^?1 of dissolved Pb in the interstitial water of the hyporheic zone may be a major cause of the deterioration of fish habitats in the stream and be regarded as a serious risk to the target of good ecological status as defined in the European Water Framework Directive. Inundation tests provide an indication that bank sediments have the potential to contribute dissolved Pb to surface water.

Conclusions

The determination of Pb in the interstitial water and in the inundation water, taken with water Pb mass balance and sediment Pb distribution maps at the catchment scale, implicate the contaminated sediments as a large Pb supply to surface water. Assessment of these diffuse contaminant sources is critical for the successful management of mining-impacted catchments.     

Vertical distributions of PAHs in the sediments of four lakes in Japan

Purpose

The purpose of this study was to elucidate historical trends, spatial variations, and the sources of polycyclic aromatic hydrocarbons (PAHs) pollution in several Japanese lakes.

Materials and methods

The vertical distributions of PAHs in the core samples of sediments taken at several points in lakes Kasumigaura, Suwa, Kizaki, and Shinji were determined using a gas chromatograph equipped with a mass selective detector and combined with chronological information and the physical/elemental properties of the sediment.

Results and discussion

Seventeen related compounds (congeners) typically had concentration peaks at sediment depths corresponding to the 1960s to 1970s. In Lake Shinji and one bay of Lake Kasumigaura, there was a tendency for PAH concentrations to increase downstream; in contrast, another bay of Lake Kasumigaura showed the reverse trend. During big flood events, the fluxes of PAHs increased due to large inputs of particulate matter, although PAH concentrations were reduced. For the four study lakes and other similar lakes, PAH concentrations of surface sediments were approximately proportional to population densities in the respective watersheds, while the total input of PAHs to the lakes were correlated with their population and watershed area. The source apportionment analysis using isomer ratios for the congener profiles indicated that the principal sources of the PAHs in the lake sediments were gasoline and/or diesel engine exhausts and biomass burning.

Conclusions

The observed concentration peaks showed a deterioration of the chemical quality of atmospheric conditions around 1960?C1970 and a recent tendency for their amelioration. Between-lake differences suggest that the influence of human activity in the watersheds influences sediment PAH concentrations. The PAH sources were identified to be of pyrogenic origin.     

Application of ionic liquids for the extraction and passive sampling of endocrine-disrupting chemicals from sediments

Purpose

The aim of this study was to assess the applicability of ionic liquids (ILs) in the extraction of organic contaminants from sediments and in passive sampling as a receiving phase material.

Materials and methods

Solutions of two water-soluble ionic liquids (WSILs)—1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIm]BF₄) and N-butyl-3-methyl pyridinium tetrafluoroborate ([BMPy]BF₄)—were used for the extraction of endocrine-disrupting chemicals (EDCs), including bisphenol A (BPA), 17β-estradiol (E2), and nonylphenol (NP), from different sediments. Furthermore, a hydrophobic IL (1-hexadecyl-3-methyl imidazolium hexafluorophosphate) was filled in a polyethylene (PE) membrane tubing to build an IL-PE passive sampler for sediment pore water. Uptake kinetics were studied by exposing samplers to sediments artificially contaminated by EDCs and identified by exposing samplers to field-contaminated sediments.

Results and discussion

EDCs were efficiently extracted by WSIL solutions from the two artificially contaminated sediments, with maximum extraction efficiencies of 84.2–104.6 % by the [BMIm]BF₄ solution and 74.9–103.7 % by the [BMPy]BF₄ solution. However, WSIL solutions are not suitable for EDC extraction from sediment with very low organic carbon contents. EDCs in sediment pore water can be efficiently taken up by the IL-PE sampler, with uptake rate constants of 2.08?×?10^?2?l?g^?1?day^?1 (BPA), 5.74?×?10^?2?l?g^?1?day^?1 (E2), and 2.10 l?g^?1?day^?1(NP).

Conclusion

BPA, E2, and NP can be extracted efficiently by IL water solution from most of the artificially and field-contaminated sediments used in this study. The IL ([HDMIm]PF₆)-PE passive sampler can be used to monitor EDCs in the pore water of sediments. A good match between the calculated and measured concentrations of BPA and E2 in pore water of field-contaminated sediments was observed.     

Mineralogy and nutrient desorption of suspended sediments during a storm event

Purpose

This study investigated desorption of potassium (K) and phosphorus (P) from soil and river suspended sediments sampled during a storm event in a Brazilian watershed traditionally used for tobacco plantations.

Material and methods

Suspended sediment samples were collected automatically at the outlet of the watershed and were grouped into three phases: beginning (phase a), middle (phase b) and final stages (phase c) of the storm event. Granulometric and mineralogical characterisation of soils (0 to 0.20 m depth) and suspended sediments was determined, and K and P extractions were performed using a cation and anion exchange resin (CAER) membrane. A kinetic modelling approach was used to estimate the amount of K and P desorbed.

Results and discussion

Clay-sized (<2 μm) content of the soils were all <21 %. Kaolinite, smectite (partially with hydroxy-Al interlayer) and a small amount of illite were found in the clay fraction of the different soils. The clay-sized fractions in sediments of phases a, b and c of the storm event were 49, 52 and 72 %, respectively. Smectite (>90 %) and kaolinite (<10 %) were the dominant clay minerals in the suspended sediments. The values of labile P and potentially available P of suspended sediments were higher than those for soils. In sediments, the highest values of labile P (325 mg kg^?1) and labile K (4,458 mg kg^?1) were found in phase c and in phase a, respectively.

Conclusions

Particle size distribution and clay mineralogy of soils differed from those of suspended sediments collected during the storm event. By comparison with the watershed soils, suspended sediments collected during the storm event were enriched in fine particles composed mainly of smectite, and this may explain their P and K desorption behaviour. This suggests particle size and clay species selectivity processes during the transfer of sediment particles from soils to aquatic systems. The amounts of P and K desorbed from the suspended sediments in the three phases of the storm event were much larger than those desorbed from soils. This indicates that rainfall promoted the transfer of these nutrients to the watercourses.     

Identification of the sources of metals and arsenic in river sediments by multivariate analysis and geochemical approaches

Purpose

Frequent mining activities and higher background values in soil have led to the contamination of the sediments of some rivers in southwest China by several metals and arsenic (As). This study combined multivariate analysis with geochemical approaches to differentiate mining activity from other sources, which may aid to evaluate the effectiveness of reducing mining release.

Materials and methods

Sixteen sediment samples were collected along the Yuan River, China. The total concentrations of lead (Pb), zinc (Zn), copper (Cu), cadmium (Cd), chromium (Cr), mercury (Hg), and As were measured by inductively coupled plasma-atomic emission spectrometer (ICP-AES). The Pb isotopic composition was measured using a thermal ionization mass spectrometer (TIMES). Both geochemical approaches and multivariate statistical analysis were used to identify the sources of these metals. The fractionation of Pb was determined through a Community Bureau of Reference (BCR) sequential extraction procedure to aid the identification of the sources.

Results and discussion

The concentrations and enrichment factors (EFs) of Pb, Zn, Cu, Cd, and As in the middle reach of the river were higher than those at the other sites, indicating anthropogenic sources. The factor analysis (FA) extracted “mining and smelting,” “mixture of anthropogenic and natural,” and “natural” factors. The Pb isotope composition of metal ores was similar (²⁰⁶Pb/²⁰⁷Pb?<?1.190 and ²⁰⁸Pb/²⁰⁶Pb?>?2.023) to that found in the sediments in the middle reach, indicating anthropogenic sources of mining activities. Compared with the narrow ranges of the δ³⁴S ratios in the bedrock (+8.5 to +9.3?‰) and the metal ores (?1.4 to +1.9?‰), the sediment samples presented a relatively wide range of δ³⁴S ratios from ?2.6 to +9.2?‰ with a mean of +2.6?‰, which suggests a mixed composition. The BCR sequential extraction procedure revealed that the proportion of the extractable fraction in the sediments in the middle reach was higher than that in other sites, suggesting anthropogenic sources as the cause of contamination in the study area.

Conclusions

Lead, Zn, Cu, Cd, Cr, Hg, and As are mainly derived from natural materials in the upstream region. In the middle reach, these elements are the result of anthropogenic activities, particularly activities associated with the mining industry. In the downstream region, the origin of these elements is considered to be a mixture of anthropogenic and natural sources. In addition to geochemical approaches and multivariate statistical analysis, the BCR sequential extraction method is an effective procedure for the identification of the anthropogenic sources of sediment-associated metals.