Irreversible phosphorus sorption in septic system plumes?

The mobility of phosphorus (P) in septic system plumes remains a topic of debate because of the considerable reactivity of this constituent. In this study, a septic system plume in Ontario was monitored over a 16-year period with detail that clearly shows the advancing frontal portion of the P plume. This monitoring record provides insight into the extent of secondary P attenuation in the ground water zone beyond that available from previous studies. A P plume 16 m in length developed over the monitoring period with PO(4)-P concentrations (3 to 6 mg/L) that approached the concentrations present under the tile bed. Simulations using an analytical model showed that when first-order solute decay was considered to account for the possibility of secondary P attenuation in the ground water zone, field values could only be matched when decay was absent or occurred at an exceedingly slow rate (half-life greater than 30 years). Thus, hypothesized secondary P attenuation mechanisms such as slow recystallization of sorbed P into insoluble metal phosphate minerals, diffusion into microsites, or kinetically slow direct precipitation of P minerals such as hydroxyapatite were inactive in the ground water zone at this site or occurred at rates that were too slow to be observed in the context of the current 16-year study. Desorption tests on sediment samples from below the tile bed indicated a PO(4) distribution coefficient (K(d)) of 4.8, which implies a P retardation factor of 25, similar to the field apparent value of 37 determined from model calibrations. This example of inactive secondary P attenuation in the ground water zone shows that phosphorus in some ground water plumes can remain mobile and conservative for decades. This has important implications for septic systems located in lakeshore environments when long-term usage scenarios are considered.     

Natural attenuation of septic system nitrogen by anammox

On-site disposal of sewage in septic systems can lead to groundwater plumes with NO(3)(-)-N concentrations exceeding the common drinking water limit of 10 mg/L. Currently, denitrification is considered as the principal natural attenuation process. However, at a large seasonal-use septic system in Ontario (256 campsites), a suboxic zone exists where nitrogen removal of up to 80% occurs including removal of NH(4)(+)-N. This zone has both NO(3)(-)-N and NH(4)(+)-N at >5 mg/L each. In the distal NH(4)(+)-rich zone, NH(4)(+)-N concentrations (8.1 ± 8.0 mg/L) are lower than in the proximal zone (48 ± 36 mg/L) and NH(4)(+)-N is isotopically enriched (concentration-weighted mean δ(15)N of +15.7‰) compared to the proximal zone (+7.8‰). Furthermore, δ(15)N-NH(4)(+) isotopic enrichment increases with depth in the distal zone, which is opposite to what would result if nitrification along the water table zone was the mechanism causing NH(4)(+) depletion. Bacterial community composition was assessed with molecular (DNA-based) analysis and demonstrated that groundwater bacterial populations were predominantly composed of bacteria from two Candidatus genera of the Planctomycetales (Brocadia and Jettenia). Together, these data provide strong evidence that anaerobic ammonium oxidation (anammox) plays an important role in nitrogen attenuation at this site.     

Denitrification and Phosphate Removal in Experiments Using Al Stearate

Hydrophobic Al monostearate was tested as a low-solubility denitrification substrate for anaerobic bacteria and a source of aluminum for phosphate precipitation. Flow-through laboratory columns at 25 ± 2°C were used with O₂-saturated solutions containing 1x, 2x, 8x, and 16x concentrations of 2.26 mg/L NO₃-N and 3.26 mg/L PO₄-P. Denitrification was exponential, approximating first-order reaction kinetics with the rate constant being a function of the initial nitrate concentration. The half life in minutes can be approximated by 5.29 (mg/L NO₃- N°)^1/2 where NO₃-N° was the initial input nitrate concentration. The reaction times were significantly shorter than those required using Ca distearate as a carbon source and much shorter than those using cellulose (white pine shavings) as a carbon source. Al stearate has potential for use in a flow-through container for denitrification of oxidized effluent from home sewage systems.
Aqueous phosphate removal with Al stearate depended upon dissolution of the Al stearate followed by precipitation of Al phosphate. Only 5% to 10% of the phosphate was removed from the solution. The amounts removed were similar to those obtained using bauxite grains as an aluminum source, following saturation of sorption sites with phosphate on bauxite. Aqueous phosphate removal with Ca stearate was insignificant, as the released calcium was apparently precipitated as calcite rather than as hydroxyapatite.     

Use of an Artificial Sweetener to Identify Sources of Groundwater Nitrate Contamination

The artificial sweetener acesulfame (ACE) is a potentially useful tracer of waste water contamination in groundwater. In this study, ACE concentrations were measured in waste water and impacted groundwater at 12 septic system sites in Ontario, Canada. All samples of septic tank effluent (n = 37) had ACE >6 µg/L, all samples of groundwater from the proximal plume zones (n = 93) had ACE >1 µg/L and, almost all samples from the distal plume zones had ACE >2 µg/L. Mean mass ratios of total inorganic nitrogen/ACE at the 12 sites ranged from 680 to 3500 for the tank and proximal plume samples. At five sites, decreasing ratio values in the distal zones indicated nitrogen attenuation. These ratios were applied to three aquifers in Canada that are nitrate‐stressed and an urban stream where septic systems are present nearby to estimate the amount of waste water nitrate contamination. At the three aquifer locations that are agricultural, low ACE values (<0.02‐0.15 µg/L) indicated that waste water contributed <15% of the nitrate in most samples. In groundwater discharging to the urban stream, much higher ACE values (0.2‐11 µg/L) indicated that waste water was the likely source of >50% of the nitrate in most samples. This study confirms that ACE is a powerful tracer and demonstrates its use as a diagnostic tool for establishing whether waste water is a significant contributor to groundwater contamination or not.     

Major Ion and Trace Metal Geochemistry of an Acidic Septic-System Plume in Silt

Four years of detailed ground-water monitoring at a newly installed, seasonal-use, domestic septic system located on poorly buffered (CaCO₃ equivalent content ≤ 1.6 wt.%) lacustrine silt, has revealed the development of an acidic ground-water plume. Acid, generated by the partial oxidation of effluent NH₄⁺ dissolved organic carbon (DOC), and possibly sulfide minerals present in the sediment, has resulted in a distal plume core zone with pH values in the range of 4.4 to 5.0. The acidic zone, where NH₄⁺ does, however, persist (> 2 mg/1, as N) and where DOC remains elevated (6–13 mg/1), is associated with high average concentrations of the trace metals Fe (4.7 mg/1), Al (1.9 mg/1), and Mn (3.6 mg/1). Attenuation of nitrogen along the plume core flowpath is indicated by a decrease in the N/ Cl⁻ ratio from an effluent value of 1.7, to a plume value of only 0.5 after 4 m of subsurface flow. Increased SO₄²⁻ levels observed in the zone of N depletion suggest that attenuation can be at least partly attributed to reduction of plume NO₃⁻ by oxidation of reduced S present in the sediment. PO₄³⁻ has not migrated significantly beyond the infiltration bed gravel layer, demonstrating that PO₄³⁻ mobility is limited in these sediments (retardation factor > 10).     

Temperature, density and buoyancy fluxes in “black smoker” plumes, and the criterion for buoyancy reversal

Measurements of the temperature and composition of effluent from vents on the sea floor can be used to deduce the in-situ density of this fluid, which is required for calculations of flow in the chimneys and through their porous walls. This density is, however, not directly relevant when calculating the buoyancy flux in the plume above a smoker. It is the asymptotic buoyancy flux, following extensive dilution with seawater, which is required when estimating the height of rise of plumes in a stably stratified ocean, and when calculating the criterion for reversal of buoyancy due to non-linear mixing effects. The results of mixing calculations show that the effluent from hydrothermal vents on the sea floor will exhibit reversing buoyancy if the ejected fluid has a temperature of 300°C and a salinity greater than 8 wt.% NaCl. If the temperature of the effluent is 200°C the salinity required for reversing buoyancy falls to 5.5 wt.% NaCl. Measurements of temperature and salinities of sea-floor hydrothermal fluid suggest that fluids with the characteristics required to form reversing plumes are ejected at the sea floor. The possibility that reversing plumes may be found has important implications for the formation of massive sulfide deposits.     

Microplastic Contamination in Karst Groundwater Systems

Groundwater in karst aquifers constitutes about 25% of drinking water sources globally. Karst aquifers are open systems, susceptible to contamination by surface-borne pollutants. In this study, springs and wells from two karst aquifers in Illinois, USA, were found to contain microplastics and other anthropogenic contaminants. All microplastics were fibers, with a maximum concentration of 15.2 particles/L. The presence of microplastic was consistent with other parameters, including phosphate, chloride and triclosan, suggesting septic effluent as a source. More studies are needed on microplastic sources, abundance, and impacts on karst ecosystems.     

Pyrite Oxidation Halts Migration of a Phosphorus Plume

We have established a monitoring record of phosphate (PO₄³⁻) migration in the Long Point, ON campground septic system plume that now spans 26 years. Previously, at year 16 (2006), a P plume 16 m in length was documented and provided a good fit with an analytical advection dispersion model when a P migration velocity of 0.8 m/yr was used (retardation factor of 37) and when P behaved in an otherwise conservative manner (sorption only). However, between years 16 and 26 (2016), the P plume length expanded by only 2 m (0.2 m/yr) and increased in depth by only 0.5 m. The zone of abrupt P depletion at depth occurs close to the zone where SO₄²⁻ concentrations increase in response to NO₃⁻ oxidation of pyrite. Scanning electron microscope images of sand grains from the nose of the P plume reveal abundant authigenic mineral coatings of considerable thickness (∼5 to 20 μm), with Fe as the dominant cation and containing 1 to 3 wt % P. This evidence suggests that P is now being attenuated along a reaction front that coincides with the zone where pyrite oxidation is occurring. P migration may now be controlled by the rate of migration of the pyrite oxidation front and this is several times slower than the previously indicated rate in the shallower, sorption-controlled portion of the plume. Monitoring at Long Point has demonstrated the danger of embracing an overly simplistic conceptual model when attempting to predict wastewater P migration in groundwater and also highlights the unique insight provided by a long-term monitoring record.     

Variations in Phosphorus Speciation in Response to Simulated Riparian Zone Enhancement with Red Mud to Treat Reclaimed Water

Variations in phosphorus speciation in two sets of simulated riparian zones with and without Perennial ryegrass were compared. Each set consisted of four units, each measuring 700 mm × 200 mm × 200 mm, which were enhanced with 0, 2.5, 5, and 7.5% red mud (RM) by weight. The levels of total phosphorus (TP), total dissolved phosphorus (TDP), soluble reactive phosphorus (SRP) in the effluent were analyzed, and phosphorus fractionation in the media were also determined after the systems had been operational for 3 months. The results showed that the unit received 2.5% RM had the highest rate of phosphorus removal, including TP, TDP, SRP, particulate phosphorus (PP), and dissolved organic phosphorus (DOP) were present at the average concentrations of 0.17, 0.10, 0.07, 0.08, and 0.03 mg/L in the effluent. Sequential phosphorus fractionation showed that calcium‐bound phosphorus (Ca–P) was the major component, indicating that the addition of RM induced aluminum/iron‐bound phosphorus (Al/Fe–P), which was intensely bioactive, to form intractable Ca–P, which further inhibited the release of phosphorus from the media. However, the presence of P. ryegrass had little effect on the removal of phosphorus. Therefore, RM, when used directly in riparian zones at a suitable concentration, is a novel and low cost additive material that can be used to remove phosphorus from reclaimed water.     

Phosphorus retention in constructed wetlands enhanced by zeolite- and clinopyroxene-dominated lava sand

Constructed wetlands (CWs) are engineered systems for treating wastewater by sequestering nutrients and contaminants. Our aim was to assess the main phosphorus (P) binding states in operating CWs to assess P saturation and indications on P recycling potential of filter materials, which might be necessary under future peak P scenarios. The investigated vertical flow CWs (operation time up to 16 years) are based on either fluviatile (Fluv) sand or zeolite- (Ze-LS) and clinopyroxene (Cl-LS)-dominated lava sand. Organic and inorganic P accumulated in all CWs independent of filter materials and showed a considerable increase with operation time. Concentrations of P decreased sharply with depth in the Fluv-CWs compared to only a slight decrease in the lava sand CWs, with P concentrations of deeper horizons approximating the relatively P enriched original lava sand substrates. Orthophosphate was the dominant pool in all CWs, while the sum of organic fractions ranged between 11% and 33%. Sequential extraction indicated that P was mainly associated with Fe and Al (hydr)oxides for Fluv-CWs and Ze-LS-CWs, while Ca and Mg bound mineral phosphates dominated in Cl-LS-CWs. Oxalate extractions pointed to a clear dominance of P fractions associated with poorly crystalline Fe- and Al-(oxy)hydroxides. Solution ³¹P NMR analyses revealed that inositol hexakisphosphates were a major pool of organic P in surface layers of CWs, which increased with operation time. With a maximum of 0.5% P content, filter sands do not appear to be a suitable fertilizer for direct application to agricultural fields. The dominance of inorganic, poorly crystalline P species point to potentially high desorption capacity which might be investigated further, to assess recycling potential of P or usage of filter materials as soil amendments with relatively high plant available P. The latter might become feasible and economically attractive under future P scarcity. Simultaneously, P saturation indexes (DPS) did not indicate an imminent P saturation of filters, since P accumulation was not restricted by binding to Al and Fe minerals.     

Model parameters for simulating fate and transport of on-site wastewater nutrients

This paper presents a critical review of model-input parameters for transport of on-site wastewater treatment system (OWS) pollutants. Approximately 25% of the U.S. population relies on soil-based OWS for effective treatment and protection of public health and environmental quality. Mathematical models are useful tools for understanding and predicting the transport and fate of wastewater pollutants and for addressing water-budget issues related to wastewater reclamation from site to watershed scales. However, input parameters for models that simulate fate and transport of OWS pollutants are not readily obtained. The purpose of this analysis is to illustrate an objective, statistically supported method for choosing model-input parameters related to nitrogen (N) and phosphorus (P). Data were gathered from existing studies reported in the literature. Cumulative frequency distributions (CFDs) are provided for OWS effluent concentrations of N and P, nitrification and denitrification rates, and linear sorption isotherm constants for P. When CFDs are not presented, ranges and median values are provided. Median values for model-input parameters are as follows: total N concentration (44 mg/L), nitrate-N (0.2 mg/L), ammonium (60 mg/L), phosphate-P (9 mg/L), organic N (14 mg/L), zero-order nitrification rate (264 mg/L/d), first-order nitrification (2.9/d), first-order dentrification (0.025/d), maximum soil capacity for P uptake (237 mg/kg), linear sorption isotherm constant for P (15.1 L/kg), and OWS effluent flow rates (260 L/person/d).     

Estimating background and threshold nitrate concentrations using probability graphs

Because of the ubiquitous nature of anthropogenic nitrate (NO3(-)) in many parts of the world, determining background concentrations of NO3(-) in shallow ground water from natural sources is probably impossible in most environments. Present-day background must now include diffuse sources of NO3(-) such as disruption of soils and oxidation of organic matter, and atmospheric inputs from products of combustion and evaporation of ammonia from fertilizer and livestock waste. Anomalies can be defined as NO3(-) derived from nitrogen (N) inputs to the environment from anthropogenic activities, including synthetic fertilizers, livestock waste, and septic effluent. Cumulative probability graphs were used to identify threshold concentrations separating background and anomalous NO(3)-N concentrations and to assist in the determination of sources of N contamination for 232 spring water samples and 200 well water samples from karst aquifers. Thresholds were 0.4, 2.5, and 6.7 mg/L for spring water samples, and 0.1, 2.1, and 17 mg/L for well water samples. The 0.4 and 0.1 mg/L values are assumed to represent thresholds for present-day precipitation. Thresholds at 2.5 and 2.1 mg/L are interpreted to represent present-day background concentrations of NO(3)-N. The population of spring water samples with concentrations between 2.5 and 6.7 mg/L represents an amalgam of all sources of NO3(-) in the ground water basins that feed each spring; concentrations > 6.7 mg/L were typically samples collected soon after springtime application of synthetic fertilizer. The 17 mg/L threshold (adjusted to 15 mg/L) for well water samples is interpreted as the level above which livestock wastes dominate the N sources.     

Nitrogen Attenuation in Septic System Plumes

The persistence of inorganic nitrogen is assessed in a set of 21 septic system plumes located in Ontario, Canada, that were studied over a 31-year period from 1988 to 2019. In the plume zones underlying the drainfields, site mean NO₃⁻ values averaged 34 ± 27 mg N/L and exceeded the nitrate drinking water limit (DWL) of 10 mg N/L at 16 of 21 sites. In plume zones extending up to 30 m downgradient from the drainfields, site mean NO₃⁻ values averaged 24 ± 20 mg N/L and exceeded the DWL at 9 of 13 sites. Site mean total inorganic nitrogen (TIN; NH₄⁺ + NO₃⁻ − N) removal averaged 34 ± 26% in the drainfield zones and 36 ± 44% in the downgradient plume zones, indicating that much of the removal occurred within the drainfields. Removal was much higher at nine sites where drainfield TIN included >10% NH₄⁺ (62 ± 25% removal). TIN removal was not correlated with wastewater loading rate, system age, or sediment carbonate mineral content, but was correlated with water table depth, where shallower water table sites had generally less complete wastewater oxidation. At many of these sites, both NO₃⁻ and NH₄⁺ were present together in the plumes and were lost concomitantly, suggesting that the anammox reaction was making an important contribution to the observed TIN loss. When groundwater nitrate contamination is a concern, considering on-site treatment system designs that lead to a lesser degree of wastewater oxidation, could be a useful approach for enhancing N removal.     

Biogeochemical evolution of a landfill leachate plume, Norman, Oklahoma

Leachate from municipal landfills can create groundwater contaminant plumes that may last for decades to centuries. The fate of reactive contaminants in leachate-affected aquifers depends on the sustainability of biogeochemical processes affecting contaminant transport. Temporal variations in the configuration of redox zones downgradient from the Norman Landfill were studied for more than a decade. The leachate plume contained elevated concentrations of nonvolatile dissolved organic carbon (NVDOC) (up to 300 mg/L), methane (16 mg/L), ammonium (650 mg/L as N), iron (23 mg/L), chloride (1030 mg/L), and bicarbonate (4270 mg/L). Chemical and isotopic investigations along a 2D plume transect revealed consumption of solid and aqueous electron acceptors in the aquifer, depleting the natural attenuation capacity. Despite the relative recalcitrance of NVDOC to biodegradation, the center of the plume was depleted in sulfate, which reduces the long-term oxidation capacity of the leachate-affected aquifer. Ammonium and methane were attenuated in the aquifer relative to chloride by different processes: ammonium transport was retarded mainly by physical interaction with aquifer solids, whereas the methane plume was truncated largely by oxidation. Studies near plume boundaries revealed temporal variability in constituent concentrations related in part to hydrologic changes at various time scales. The upper boundary of the plume was a particularly active location where redox reactions responded to recharge events and seasonal water-table fluctuations. Accurately describing the biogeochemical processes that affect the transport of contaminants in this landfill-leachate-affected aquifer required understanding the aquifer's geologic and hydrodynamic framework.     

Natural Attenuation of Perchlorate in Denitrified Groundwater

Monitoring of a well‐defined septic system groundwater plume and groundwater discharging to two urban streams located in southern Ontario, Canada, provided evidence of natural attenuation of background low level (ng/L) perchlorate (ClO₄^?) under denitrifying conditions in the field. The septic system site at Long Point contains ClO₄^? from a mix of waste water, atmospheric deposition, and periodic use of fireworks, while the nitrate plume indicates active denitrification. Plume nitrate (NO₃^?‐N) concentrations of up to 103 mg/L declined with depth and downgradient of the tile bed due to denitrification and anammox activity, and the plume was almost completely denitrified beyond 35 m from the tile bed. The ClO₄^? natural attenuation occurs at the site only when NO₃^?‐N concentrations are <0.3 mg/L, after which ClO₄^? concentrations decline abruptly from 187 ± 202 to 11 ± 15 ng/L. A similar pattern between NO₃^?‐N and ClO₄^? was found in groundwater discharging to the two urban streams. These findings suggest that natural attenuation (i.e., biodegradation) of ClO₄^? may be commonplace in denitrified aquifers with appropriate electron donors present, and thus, should be considered as a remediation option for ClO₄^? contaminated groundwater.     

The distribution of trace metals in Florida Bay sediments

The distribution of trace metals based on surface sediments collected at 40 stations across Florida Bay was done in June, November and February 2000-2001. Concentrations of Sc, V, Ba, Cd, Cr, Co, Cu, Pb, Mn, Ni, Zn, Al and Mg were determined by ICP-MS, and the total Fe was determined by spectrophotometry. Organic carbon (OC), nitrogen (N), and calcium carbonate (CaCO3) were also measured. Eleven of 13 metals showed a similar distribution pattern for the various months studied. Maximum concentrations of metals were lower than those found in most estuarine systems and were concentrated in the north-central and western zones of the Bay. The Mn and Fe concentrations, unlike the other metals, gradually decreased from north (Everglades) to south (Florida Keys). Some metals (Ni, Zn, Cu, Cr, Pb and Ba) associated with petroleum use showed high concentrations at stations near the Tavernier marina. Florida Bay sediments are predominately CaCO3 (65.9-92.5%). The greatest value for OC (5.5%) and the lowest value of CaCO3 (65.9%) were found in the western zone. Trace metal distribution patterns are similar to the OC and N in the sediments. There was a strong correlation between most metals (V>Cu>Ni>Cr>Al>Co>Ba>Zn>Pb>Mg) and the percentage of OC. The maximum C/N values (9-12) were observed at the stations with the highest OC, where dense colonies of seagrass are found and most of the metals are concentrated. All metals except Mg, Mn and Co showed a strong correlation with Al and the fine fraction of the sediments (aluminosilicates) associated with continental input and river runoff.     

Verhalten ausgewählter Arzneimittel bei der künstlichen Grundwasseranreicherung – Eliminierung und Effekte auf die mikrobielle Besiedlung

Behaviour of Some Pharmaceuticals during Artificial Groundwater Recharge – Elimination and Effects on Microbiology The behaviour of bezafibrate, carbamazepine, clofibric acid, diclofenac, ibuprofen, and gemfibrozil during artificial groundwater recharge was investigated with different test systems simulating field conditions. The given concentrations of the pharmaceuticals were 100 μg/L in the influent of the systems. Concentrations in the influent as well as in the effluent were measured by GC‐MS. These column experiments indicated a significant elimination of bezafibrate, diclofenac, and ibuprofen (60 to 80%) during slow sand filtration. The results showed a moderate elimination of clofibric acid and gemfibrozil (40 to 60%) but a rather low elimination of carbamazepine (<40%). The adaptation times until the elimination processes started were about 5 days. Only the elimination of carbamazepine needed a lag phase up to 17 days. Additional column experiments with groundwater model systems indicated a high persistence of pharmaceuticals under aerobic and anaerobic groundwater conditions. The elimination was less than 20%. Only diclofenac was eliminated with rates between 60% and 80% in aerobic systems and between 40% and 60% in anaerobic systems. Analysis of eubacterial 16S‐rDNA by PCR and DGGE demonstrated changes in the microbial community structure in slow sand filters after application of pharmaceuticals. Adaptation processes may cause these changes, e.g. the appearance or disappearance of single species. Also differences between the populations of water and of the solid phase in slow sand filters could be demonstrated by DGGE pattern.     

Mass and flux distributions from DNAPL zones in sandy aquifers

At three industrial sites in Ontario, New Hampshire, and Florida, tetrachloroethylene (PCE) and trichloroethylene (TCE), released decades ago as dense nonaqueous phase liquids (DNAPLs), now form persistent source zones for dissolved contaminant plumes. These zones are suspended below the water table and above the bottoms of their respective, moderately homogeneous, unconfined sandy aquifers. Exceptionally detailed, depth-discrete, ground water sampling was performed using a direct-push sampler along cross sections of the dissolved-phase plumes, immediately downgradient of these DNAPL source zones. The total plume PCE or TCE mass-discharge through each cross section ranged between 15 and 31 kg/year. Vertical ground water sample spacing as small as 15 cm and lateral spacing typically between 1 and 3 m revealed small zones where maximum concentrations were between 1% and 61% of solubility. These local maxima are surrounded by much lower concentration zones. A spacing no larger than 15 to 30 cm was needed at some locations to identify high concentration zones, and aqueous VOC concentrations varied as much as four orders of magnitude across 30 cm vertical intervals. High-resolution sampling at these sites showed that three-quarters of the mass-discharge occurs within 5% to 10% of the plume cross sectional areas. The extreme spatial variability of the mass-discharge occurs even though the sand aquifers are nearly hydraulically homogeneous. Depth-discrete field techniques such as those used in this study are essential for finding the small zones producing most of the mass-discharge, which is important for assessing natural attenuation and designing remedial options.