Raymond B. Brennan

Impact of chemical amendment of dairy cattle slurry on phosphorus, suspended sediment and metal loss to runoff from a grassland soil.

Emerging remediation technologies such as chemical amendment of dairy cattle slurry have the potential to reduce phosphorus (P) solubility and consequently reduce P losses arising from land application of dairy cattle slurry. The aim of this study was to determine the effectiveness of chemical amendment of slurry to reduce incidental losses of P and suspended sediment (SS) from grassland following application of dairy cattle slurry and to examine the effect of amendments on metal concentrations in runoff water. Intact grassed-soil samples were placed in two laboratory runoff boxes, each 200-cm-long by 22.5-cm-wide by 5-cm-deep, before being amended with dairy cattle slurry (the study control) and slurry amended with either: (i) alum, comprising 8% aluminium oxide (Al(2)O(3)) (1.11:1 aluminium (Al):total phosphorus (TP) of slurry) (ii) poly-aluminium chloride hydroxide (PAC) comprising 10% Al(2)O(3) (0.93:1 Al:TP) (iii) analytical grade ferric chloride (FeCl(2)) (2:1 Fe:TP), (iv) and lime (Ca(OH)(2)) (10:1 Ca:TP). When compared with the study control, PAC was the most effective amendment, reducing dissolved reactive phosphorus (DRP) by up to 86% while alum was most effective in reducing SS (88%), TP (94%), particulate phosphorus (PP) (95%), total dissolved phosphorus (TDP) (81%), and dissolved unreactive phosphorus (DUP) (86%). Chemical amendment of slurry did not appear to significantly increase losses of Al and Fe compared to the study control, while all amendments increased Ca loss compared to control and grass-only treatment. While chemical amendments were effective, the reductions in incidental P losses observed in this study were similar to those observed in other studies where the time from slurry application to the first rainfall event was increased. Timing of slurry application may therefore be a much more feasible way to reduce incidental P losses. Future work must examine the long-term effects of amendments on P loss to runoff and not only incidental losses.

Incidental phosphorus and nitrogen loss from grassland plots receiving chemically amended dairy cattle slurry

Chemical amendment of dairy cattle slurry has been shown to effectively reduce incidental phosphorus (P) losses in runoff; however, the effects of amendments on incidental nitrogen (N) losses are not as well documented. This study examined P and N losses in runoff during three simulated rainfall events 2, 10 and 28 days after a single application of unamended/chemically amended dairy cattle slurry. Twenty-five hydraulically isolated plots, each measuring 0.9 m by 0.4 m and instrumented with runoff collection channels, were randomly assigned the following treatments: (i) grass-only, (ii) slurry-only (the study-control), (iii) slurry amended with industrial grade liquid alum comprising 8% Al₂O₃, (iv) slurry amended with industrial grade liquid poly-aluminum chloride (PAC) comprising 10% Al₂O₃, and (v) slurry amended with lime. During the first rainfall event, lime was ineffective but alum and PAC effectively reduced dissolved reactive P (DRP) (by 95 and 98%, respectively) and total P (TP) flow-weighted-mean-concentrations (by 82 and 93%, respectively) in runoff compared to the study-control. However, flow-weighted-mean-concentrations of ammonium-N (NH₄--N) in runoff were increased with alum- (81%) and lime-treated (11%) slurry compared to the study-control whereas PAC reduced the NH₄--N by 82%. Amendments were not observed to have a significant effect on NO₃--N losses during this study. Slurry amendments reduced P losses for the duration of the study, whereas the effect of amendments on N losses was not significant following the first event. Antecedent volumetric water content of the soil or slope of the plots did not appear to affect runoff volume. However, runoff volumes (and consequently loads of P and N) were observed to increase for the chemically amended plots compared to the control and soil-only plots. This work highlights the importance of considering both P and N losses when implementing a specific nutrient mitigation measure.

Management of landfill leachate: The legacy of European Union Directives

Landfill leachate is the product of water that has percolated through waste deposits and contains various pollutants, which necessitate effective treatment before it can be released into the environment. In the last 30years, there have been significant changes in landfill management practices in response to European Union (EU) Directives, which have led to changes in leachate composition, volumes produced and treatability. In this study, historic landfill data, combined with leachate characterisation data, were used to determine the impacts of EU Directives on landfill leachate management, composition and treatability. Inhibitory compounds including ammonium (NH4-N), cyanide, chromium, nickel and zinc, were present in young leachate at levels that may inhibit ammonium oxidising bacteria, while arsenic, copper and silver were present in young and intermediate age leachate at concentrations above inhibitory thresholds. In addition, the results of this study show that while young landfills produce less than 50% of total leachate by volume in the Republic of Ireland, they account for 70% of total annual leachate chemical oxygen demand (COD) load and approximately 80% of total 5-day biochemical oxygen demand (BOD5) and NH4-N loads. These results show that there has been a decrease in the volume of leachate produced per tonne of waste landfilled since enactment of the Landfill Directive, with a trend towards increased leachate strength (particularly COD and BOD5) during the initial five years of landfill operation. These changes may be attributed to changes in landfill management practices following the implementation of the Landfill Directive. However, this study did not demonstrate the impact of decreasing inputs of biodegradable municipal waste on leachate composition. Increasingly stringent wastewater treatment plant (WWTP) emission limit values represent a significant threat to the sustainability of co-treatment of leachate with municipal wastewater. In addition, the seasonal variation in leachate production poses a risk to effective co-treatment in municipal WWTPs, as periods of high leachate production coincide with periods of maximum hydraulic loading in WWTPs.

Treatment of landfill leachate in municipal wastewater treatment plants and impacts on effluent ammonium concentrations

Landfill leachate is the result of water percolating through waste deposits that have undergone aerobic and anaerobic microbial decomposition. In recent years, increasingly stringent wastewater discharge requirements have raised questions regarding the efficacy of co-treatment of leachate in municipal wastewater treatment plants (WWTPs). This study aimed to (1) examine the co-treatment of leachate with a 5-day biochemical oxygen demand (BOD5): chemical oxygen demand (COD) ratio less than or slightly greater than 0.26 (intermediate age leachate) in municipal WWTPs (2) quantify the maximum hydraulic and mass (expressed as mass nitrogen or COD) loading of landfill leachate (as a percentage of the total influent loading rate) above which the performance of a WWTP may be inhibited, and (3) quantify the impact of a range of hydraulic loading rates (HLRs) of young and intermediate age leachate, loaded on a volumetric basis at 0 (study control), 2, 4 and 10% (volume landfill leachate influent as a percentage of influent municipal wastewater), on the effluent ammonium concentrations. The leachate loading regimes examined were found to be appropriate for effective treatment of intermediate age landfill leachate in the WWTPs examined, but co-treatment may not be suitable in WWTPs with low ammonium-nitrogen (NH4-N) and total nitrogen (TN) emission limit values (ELVs). In addition, intermediate leachate, loaded at volumetric rates of up to 4% or 50% of total WWTP NH4-N loading, did not significantly inhibit the nitrification processes, while young leachate, loaded at volumetric rates greater of than 2% (equivalent to 90% of total WWTP NH4-N loading), resulted in a significant decrease in nitrification. The results show that current hydraulic loading-based acceptance criteria recommendations should be considered in the context of leachate NH4-N composition. The results also indicate that co-treatment of old leachate in municipal WWTPs may represent the most sustainable solution for ongoing leachate treatment in the cases examined.

Agricultural Dairy Wastewaters

In Ireland, farming is an important national industry that involves approximately 270,000 people, 6.191 million cattle, 4.257 million sheep, 1.678 million pigs and 10.7 million poultry (CSO, 2006). Agriculture utilizes 64% of Ireland’s land area (Fingleton and Cushion, 1999), of which 91% is devoted to grass, silage and hay, and rough grazing (DAFF, 2003). Grassbased rearing of cattle and sheep dominates the industry (EPA, 2004). Livestock production is associated with external inputs of nutrients. Phosphorus (P) surpluses accumulate in the soil (Culleton et al., 2000) and contribute to P loss to surface and groundwater (Tunney, 1990; Regan et al., 2010). Elevated soil P status has been identified as one of the dominant P pressures in Ireland (Tunney et al., 2000). Schulte et al. (2010) showed that it may take many years for elevated soil P concentrations to be reduced to agronomically and environmentally optimum levels. The extent of these delays was predominantly related to the relative annual P-balance (P balance relative to total P reserves). While the onset of reductions in excessive soil P levels may be observed within five years, this reduction is a slow process and may take years to decades to be completed. Agricultural wastes and in particular dairy slurry and dirty water are discussed in this chapter. However, while the term ‘waste’ is commonly used for these materials, it is an unfortunate label, as it suggests that the materials have no further use and are merely a nuisance by-product of farming systems that must be managed. However, given the high nutrient contents of these materials, it is far more appropriate for them to be considered as organic fertilizers, and as such being a valuable commodity for the farmer. With higher and more volatile chemical fertilizer prices in recent years, the fertilizer replacement value in economic terms of these materials is increasing. Therefore, the management of agricultural ‘wastes’ in a manner that maximises the nutrient recovery and fertilizer value to crops should be a priority within any management plan for these materials. Nutrient contents and various research areas regarding management, remediation and control of such nutrients to prevent losses to the environment are discussed. The Surface Water Directive, 75/440/EEC (EEC, 1975), the Groundwater Directive, 80/68/EEC (EEC, 1980), the Drinking Water Directive, 98/83/EC (EC, 1998), the Nitrates Directive, 91/676/EEC (EEC, 1991(a)) and the Urban Wastewater Directive, 91/271/EEC (EEC, 1991(b)), combined with recent proceedings taken against the Irish State by the EU Commission alleging non-implementation of some aspects of the directives, has focused

Mixed Agricultural Pollutant Mitigation Using Woodchip/Pea Gravel and Woodchip/Zeolite Permeable Reactive Interceptors

Dairy soiled water (DSW) is water from concreted areas, hard stand areas and holding areas for livestock that has become contaminated by livestock faeces or urine, chemical fertilisers and parlour washings. Losses of DSW occur as point (e.g. storage, pivot irrigators) and diffuse losses (e.g. during or shortly after land application). The concept of a permeable reactive interceptor (PRI), comprising a denitrifying bioreactor woodchip cell to convert nitrate (NO3−) to dinitrogen (N2) gas and an adsorptive media cell for phosphorus (P) and ammonium (NH4+) mitigation, attempts to simultaneously treat mixed pollutants. This study is the first attempt to test this concept at laboratory-scale. Washing of woodchip media prior to PRI operation produced low NO3− but high NH4+, dissolved reactive P (DRP) and dissolved organic carbon losses. Dairy soiled water was then treated in replicated PRIs containing woodchip in combination with zeolite or gravel compartments. In general, all PRIs were highly efficient at reducing NO3−, NH4+, DRP, dissolved unreactive phosphorus (DUP) and dissolved organic nitrogen (DON) from an influent water replicating DSW. Longitudinal and hydrochemical PRI profiles, as well as zeolite batch experiments, showed that woodchip can both enhance NO3− reduction and adsorb nutrients. Since woodchip is likely to become saturated, it is important to place the reactive media cell further into the sequence of treatment. Even though the majority of the dissolved nutrients were mitigated, the PRIs also emitted greenhouse gases, which would need further remediation sequences.

Use of zeolite with alum and polyaluminum chloride amendments to mitigate runoff losses of phosphorus, nitrogen, and suspended solids from agricultural wastes applied to grassed soils

Diffuse pollutant losses containing phosphorus (P), nitrogen (N), and suspended solids (SS) can occur when agricultural wastes are applied to soil. This study aimed to mitigate P, N, and SS losses in runoff from grassed soils, onto which three types of agricultural wastes (dairy slurry, pig slurry, and dairy-soiled water [DSW]), were applied by combining amendments of either zeolite and polyaluminum chloride (PAC) with dairy and pig slurries or zeolite and alum with DSW. Four treatments were investigated in rainfall simulation studies: (i) control soil, (ii) agricultural wastes, (iii) dairy and pig slurries amended with PAC and DSW amended with alum, and (iv) dairy and pig slurries amended with zeolite and PAC and DSW amended with zeolite and alum. Our data showed that combined amendments of zeolite and PAC applied to dairy and pig slurries reduced total P (TP) in runoff by 87 and 81%, respectively, compared with unamended slurries. A combined amendment of zeolite and alum applied to DSW reduced TP in runoff by 50% compared with unamended DSW. The corresponding reductions in total N (TN) were 56% for dairy slurry and 45% for both pig slurry and DSW. Use of combined amendments reduced SS in runoff by 73 and 44% for dairy and pig slurries and 25% for DSW compared with unamended controls, but these results were not significantly different from those using chemical amendments only. The findings of this study are that combined amendments of zeolite and either PAC or alum reduce TP and TN losses in runoff to a greater extent than the use of single PAC or alum amendments and are most effective when used with dairy slurry and pig slurry but less effective when used with DSW.

The short-term effects of management changes on watertable position and nutrients in shallow groundwater in a harvested peatland forest

Management changes such as drainage, fertilisation, afforestation and harvesting (clearfelling) of forested peatlands influence watertable (WT) position and groundwater concentrations of nutrients. This study investigated the impact of clearfelling of a peatland forest on WT and nutrient concentrations. Three areas were examined: (1) a regenerated riparian peatland buffer (RB) clearfelled four years prior to the present study (2) a recently clearfelled coniferous forest (CF) and (3) a standing, mature coniferous forest (SF), on which no harvesting took place. The WT remained consistently below 0.3 m during the pre-clearfelling period. Results showed there was an almost immediate rise in the WT after clearfelling and a rise to 0.15 m below ground level (bgl) within 10 months of clearfelling. Clearfelling of the forest increased dissolved reactive phosphorus concentrations (from an average of 28-230 μg L(-1)) in the shallow groundwater, likely caused by leaching from degrading brash mats.

Zeolite combined with alum and polyaluminum chloride mixed with agricultural slurries reduces carbon losses in runoff from grassed soil boxes

Carbon (C) losses from agricultural soils to surface waters can migrate through water treatment plants and result in the formation of disinfection by-products, which are potentially harmful to human health. This study aimed to quantify total organic carbon (TOC) and total inorganic C losses in runoff after application of dairy slurry, pig slurry, or milk house wash water (MWW) to land and to mitigate these losses through coamendment of the slurries with zeolite (2.36-3.35 mm clinoptilolite) and liquid polyaluminum chloride (PAC) (10% AlO) for dairy and pig slurries or liquid aluminum sulfate (alum) (8% AlO) for MWW. Four treatments under repeated 30-min simulated rainfall events (9.6 mm h) were examined in a laboratory study using grassed soil runoff boxes (0.225 m wide, 1 m long; 10% slope): control soil, unamended slurries, PAC-amended dairy and pig slurries (13.3 and 11.7 kg t, respectively), alum-amended MWW (3.2 kg t), combined zeolite and PAC-amended dairy (160 and 13.3 kg t zeolite and PAC, respectively) and pig slurries (158 and 11.7 kg t zeolite and PAC, respectively), and combined zeolite and alum-amended MWW (72 and 3.2 kg t zeolite and alum, respectively). The unamended and amended slurries were applied at net rates of 31, 34, and 50 t ha for pig and dairy slurries and MWW, respectively. Significant reductions of TOC in runoff compared with unamended slurries were measured for PAC-amended dairy and pig slurries (52 and 56%, respectively) but not for alum-amended MWW. Dual zeolite and alum-amended MWW significantly reduced TOC in runoff compared with alum amendment only. We conclude that use of PAC-amended dairy and pig slurries and dual zeolite and alum-amended MWW, although effective, may not be economically viable to reduce TOC losses from organic slurries given the relatively low amounts of TOC measured in runoff from unamended slurries compared with the amounts applied.

The Effect of Chemical Amendments Used for Phosphorus Abatement on Greenhouse Gas and Ammonia Emissions from Dairy Cattle Slurry: Synergies and Pollution Swapping.

Land application of cattle slurry can result in incidental and chronic phosphorus (P) loss to waterbodies, leading to eutrophication. Chemical amendment of slurry has been proposed as a management practice, allowing slurry nutrients to remain available to plants whilst mitigating P losses in runoff. The effectiveness of amendments is well understood but their impacts on other loss pathways (so-called ‘pollution swapping’ potential) and therefore the feasibility of using such amendments has not been examined to date. The aim of this laboratory scale study was to determine how the chemical amendment of slurry affects losses of NH3, CH4, N2O, and CO2. Alum, FeCl2, Polyaluminium chloride (PAC)- and biochar reduced NH3 emissions by 92, 54, 65 and 77% compared to the slurry control, while lime increased emissions by 114%. Cumulative N2O emissions of cattle slurry increased when amended with alum and FeCl2 by 202% and 154% compared to the slurry only treatment. Lime, PAC and biochar resulted in a reduction of 44, 29 and 63% in cumulative N2O loss compared to the slurry only treatment. Addition of amendments to slurry did not significantly affect soil CO2 release during the study while CH4 emissions followed a similar trend for all of the amended slurries applied, with an initial increase in losses followed by a rapid decrease for the duration of the study. All of the amendments examined reduced the initial peak in CH4 emissions compared to the slurry only treatment. There was no significant effect of slurry amendments on global warming potential (GWP) caused by slurry land application, with the exception of biochar. After considering pollution swapping in conjunction with amendment effectiveness, the amendments recommended for further field study are PAC, alum and lime. This study has also shown that biochar has potential to reduce GHG losses arising from slurry application.