Differentiating nonpoint sources of deisopropylatrazine in surface water using discrimination diagrams

Pesticide degradates account for a significant portion of the pesticide load in surface water. Because pesticides with similar structures may degrade to the same degradate, it is important to distinguish between different sources of parent compounds that have different regulatory and environmental implications. A discrimination diagram, which is a sample plot of chemical data that differentiates between different parent compounds, was used for the first time to distinguish whether sources other than atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) contributed the chlorinated degradate, deisopropylatrazine (DIA; 6-chloro-N-ethyl-1,3,5-triazine-2,4-diamine) to the Iroquois and Delaware Rivers. The concentration ratio of deisopropylatrazine to deethylatrazine [6-chloro-N-(1-methylethyl)1,3,5-triazine-2,4-diamine], called the D2R, was used to discriminate atrazine as a source of DIA from other parent sources, such as cyanazine (2-[[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino]-2-methylpropionitrile) and simazine (6-chloro-N,N'-diethyl-1,3,5-triazine-2,4diamine). The ratio of atrazine to cyanazine (ACR) used in conjunction with the D2R showed that after atrazine, cyanazine was the main contributor of DIA in surface water. The D2R also showed that cyanazine, and to a much lesser extent simazine, contributed a considerable amount (approximately 40%) of the DIA that was transported during the flood of the Mississippi River in 1993. The D2R may continue to be a useful discriminator in determining changes in the nonpoint sources of DIA in surface water as cyanazine is currently being removed from the market.     

The release of phosphorus to porewater and surface water from river riparian sediments

Sediments can be both a source and a sink of dissolved phosphorus (P) in surface water and shallow groundwater. Using laboratory mesocosms, we studied the influence of flooding with deionized water and simulated river water on P release to solution using sediment columns taken from a riparian wetland. The mesocosm incubation results showed that rather than retaining nutrients, sediments in the riparian zone may be a significant source of P. Concentrations of dissolved P in porewater reached more than 3 mg L(-1) and in surface water over 0.8 mg L(-1) within a month of sediment inundation. The reductive dissolution of P-bearing iron (Fe) oxides was the likely mechanism responsible for P release. Dissolved P to Fe molar ratios in anaerobic samples were approximately 0.45 when columns were flooded with water that simulated the chemistry of the adjacent river. This suggests there was insufficient Fe in the anaerobic samples to precipitate all P if the solutions were oxygenated or transported to an aerobic environment. If the anaerobic wetland solutions were delivered to oxygenated rivers and streams adjacent to the riparian zone, the equilibrium concentration of P in these systems could rise. The timing of P release was inversely related to the nitrate (NO3-) concentration in floodwater. This indicates that in riparian zones receiving low nitrate loads, or where NO3- loads are being progressively reduced, the risk of dissolved P release may increase. These findings present particular challenges for restoration and management in riparian areas.     

Iron and aluminium based adsorption strategies for removing arsenic from water

Arsenic is a commonly occurring toxic metal in natural systems and is the root cause of many diseases and disorders. Occurrence of arsenic contaminated water is reported from several countries all over the world. A great deal of research over recent decades has been motivated by the requirement to lower the concentration of arsenic in drinking water and the need to develop low cost techniques which can be widely applied for arsenic removal from contaminated water. This review briefly presents iron and aluminium based adsorbents for arsenic removal. Studies carried out on oxidation of arsenic(III) to arsenic(V) employing various oxidising agents to facilitate arsenic removal are briefly mentioned. Effects of competing ions, As:Fe ratios, arsenic(V) vs. arsenic(III) removal using ferrihydrite as the adsorbent have been discussed. Recent efforts made for investigating arsenic adsorption on iron hydroxides/oxyhydroxides/oxides such as granular ferric hydroxide, goethite, akaganeite, magnetite and haematite have been reviewed. The adsorption behaviours of activated alumina, gibbsite, bauxite, activated bauxite, layered double hydroxides are discussed. Point-of-use adsorptive remediation methods indicate that Sono Arsenic filter and Kanchan™ Arsenic filter are in operation at various locations of Bangladesh and Nepal. The relative merits and demerits of such filters have been discussed. Evaluation of kits used for at-site arsenic estimation by various researchers also forms a part of this review.     

Remediation technologies for heavy metal contaminated groundwater

The contamination of groundwater by heavy metal, originating either from natural soil sources or from anthropogenic sources is a matter of utmost concern to the public health. Remediation of contaminated groundwater is of highest priority since billions of people all over the world use it for drinking purpose. In this paper, thirty five approaches for groundwater treatment have been reviewed and classified under three large categories viz chemical, biochemical/biological/biosorption and physico-chemical treatment processes. Comparison tables have been provided at the end of each process for a better understanding of each category. Selection of a suitable technology for contamination remediation at a particular site is one of the most challenging job due to extremely complex soil chemistry and aquifer characteristics and no thumb-rule can be suggested regarding this issue. In the past decade, iron based technologies, microbial remediation, biological sulphate reduction and various adsorbents played versatile and efficient remediation roles. Keeping the sustainability issues and environmental ethics in mind, the technologies encompassing natural chemistry, bioremediation and biosorption are recommended to be adopted in appropriate cases. In many places, two or more techniques can work synergistically for better results. Processes such as chelate extraction and chemical soil washings are advisable only for recovery of valuable metals in highly contaminated industrial sites depending on economical feasibility.     

Estimating dissolved reactive phosphorus concentration in surface runoff water from major Ontario soils

Phosphorus (P) loss from agricultural land in surface runoff can contribute to eutrophication of surface water. This study was conducted to evaluate a range of environmental and agronomic soil P tests as indicators of potential soil surface runoff dissolved reactive P (DRP) losses from Ontario soils. The soil samples (0- to 20-cm depth) were collected from six soil series in Ontario, with 10 sites each to provide a wide range of soil test P (STP) values. Rainfall simulation studies were conducted following the USEPA National P Research Project protocol. The average DRP concentration (DRP30) in runoff water collected over 30 min after the start of runoff increased (p < 0.001) in either a linear or curvilinear manner with increases in levels of various STPs and estimates of degree of soil P saturation (DPS). Among the 16 measurements of STPs and DPSs assessed, DPS(M3) 2 (Mehlich-3 P/[Mehlich-3 Al + Fe]) (r2 = 0.90), DPS(M3)-3 (Mehlich-3 P/Mehlich-3 Al) (r2 = 0.89), and water-extractable P (WEP) (r2 = 0.89) had the strongest overall relationship with runoff DRP30 across all six soil series. The DPS(M3)-2 and DPS(M3)-3 were equally accurate in predicting runoff DRP30 loss. However, DPS(M3)-3 was preferred as its prediction of DRP30 was soil pH insensitive and simpler in analytical procedure, ifa DPS approach is adopted.     

Tool for assessment of process importance at the groundwater/surface water interface

The groundwater/surface water interface (GWSWI) represents an important transition zone between groundwater and surface water environments that potentially changes the nature and flux of contaminants exchanged between the two systems. Identifying dominant and rate-limiting contaminant transformation processes is critically important for estimating contaminant fluxes and compositional changes across the GWSWI. A new, user-friendly, spreadsheet- and Visual Basic-based analytical screening tool that assists in evaluating the dominance of controlling kinetic processes across the GWSWI is presented. Based on contaminant properties, first-order processes that may play a significant role in solute transport/transformation are evaluated in terms of a ratio of process importance (P_i) that relates the process rate to the rate of fluid transfer. Besides possessing several useful compilations of contaminant and process data, the screening tool also includes 1-D analytical models that assist users in evaluating contaminant transport across the GWSWI. The tool currently applies to 29 organics and 10 inorganics of interest within the context of the GWSWI. Application of the new screening tool is demonstrated through an evaluation of natural attenuation at a site with trichloroethylene and 1,1,2,2-tetrachloroethane contaminated groundwater discharging into wetlands.     

Colloidal phosphorus in surface runoff and water extracts from semiarid soils of the western United States

Colloidal particles in runoff may have an important role in P transfer from soils to waterbodies, but remain poorly understood. We investigated colloidal molybdate-reactive phosphorus (MRP) in surface runoff and water extracts of calcareous arable soils from the semiarid western United States. Colloidal MRP was determined by ultrafiltration and operationally defined as MRP associated with particles between 1 microm and 1 nm diameter, although a smaller pore-size filter (0.3 nm) was used to define the lower size limit of colloids in water extracts. In surface runoff from three calcareous soils generated by simulated sprinkler irrigation, colloidal MRP concentrations ranged between 0.16 and 3.07 microM, constituting between 11 and 56% of the MRP in the <1-microm fraction. Concentrations were strongly correlated with agronomic and environmental soil-test P concentrations for individual soils. Water extracts of a range of similar soils contained two size fractions of colloidal MRP: a larger fraction (1.0-0.2 microm) probably associated with fine clays, and a smaller fraction (3-0.3 nm) probably associated with Ca-phosphate minerals. Colloidal MRP was solubilized in the acidic medium of the colorimetric detection procedure, suggesting that a fraction of the filterable MRP in runoff from calcareous soils may not be as readily bioavailable as free phosphate in waterbodies. Our results suggest that colloidal MRP is an important but poorly understood component of P transfer in runoff from calcareous western U.S. soils and should be given greater consideration in mechanistic studies of the P transfer process.     

Assessing the pollutional load from nonpoint sources: Planning considerations and a description of an automated water quality monitoring program

Planning considerations to be evaluated early in the design of water quality monitoring programs are reviewed. These criteria emphasize the importance of isolating the study area, parameter section, and type of measurements required to ensure meaningful results. A demonstration automatic water quality monitoring program is described. Details with respect to type of equipment, coordination of component parts, sampling program, and analysis of specific parameters are reviewed. General costs of implementation and maintenance of such programs are presented.     

Conservation tillage: best management practice for nonpoint runoff

Decisionmakers are in the process of selecting remedial measures for controlling nonpoint pollution runoff. Conservation tillage (CT) is being looked to as one of the major recommended practices. Many different systems exist and vary in the amount of crop residue left and soil roughness produced. Therefore, varying results occur in terms of yield and potential water quality impacts. Differences vary with type of tillage system, soils, geographic region, and the farmer's management. The purpose of this review is to provide material to decisionmakers that points out the assets and liabilities of the various CT systems. Tillage effects on soil characteristics and plant growth are presented and include a discussion of soil moisture and temperature, weed and insect control, nutrient availability, and yields. Water quality aspects are addressed through a discussion of the effects CT systems have on sediment, water, pesticide, and phosphorus loss.This work was supported by the Soil Science Department, College of Agriculture and Life Sciences, University of Wisconsin-Madison, and the U.S. Environmental Protection Agency, Region V, Chicago, Illinois. (Grant No. G005139-01).     

Agroforestry buffers for nonpoint source pollution reductions from agricultural watersheds

Despite increased attention and demand for the adoption of agroforestry practices throughout the world, rigorous long-term scientific studies confirming environmental benefits from the use of agroforestry practices are limited. The objective was to examine nonpoint-source pollution (NPSP) reduction as influenced by agroforestry buffers in watersheds under grazing and row crop management. The grazing study consists of six watersheds in the Central Mississippi Valley wooded slopes and the row crop study site consists of three watersheds in a paired watershed design in Central Claypan areas. Runoff water samples were analyzed for sediment, total nitrogen (TN), and total phosphorus (TP) for the 2004 to 2008 period. Results indicate that agroforestry and grass buffers on grazed and row crop management sites significantly reduce runoff, sediment, TN, and TP losses to streams. Buffers in association with grazing and row crop management reduced runoff by 49 and 19%, respectively, during the study period as compared with respective control treatments. Average sediment loss for grazing and row crop management systems was 13.8 and 17.9 kg ha yr, respectively. On average, grass and agroforestry buffers reduced sediment, TN, and TP losses by 32, 42, and 46% compared with the control treatments. Buffers were more effective in the grazing management practice than row crop management practice. These differences could in part be attributed to the differences in soils, management, and landscape features. Results from this study strongly indicate that agroforestry and grass buffers can be designed to improve water quality while minimizing the amount of land taken out of production.     

Approximating phosphorus release from soils to surface runoff and subsurface drainage

Phosphorus application in excess of crop needs has increased the concentration of P in surface soil and runoff and led many states to develop P-based nutrient management strategies. However, insufficient data are available relating P in surface soil, surface runoff, and subsurface drainage to develop sound guidelines. Thus, we investigated P release from the surface (0-5 cm depth) of a Denbigh silt loam from Devon, U.K. (30-160 mg kg-1 Olsen P) and Alvin, Berks, Calvin, and Watson soils from Pennsylvania (10-763 mg kg-1 Mehlich-3 P) in relation to the concentration of P in surface runoff and subsurface drainage. A change point, where the slopes of two linear relationships between water- or CaCl2-extractable soil P and soil test phosphorus (STP) (Olsen or Mehlich-3) meet, was evident for the Denbigh at 33 to 36 mg kg-1 Olsen P, and the Alvin and Berks soils at 185 to 190 mg Mehlich-3 P kg-1. Similar change points were also observed when STP was related to the P concentration of surface runoff (185 mg kg-1) and subsurface drainage (193 mg kg-1). The use of water and CaCl2 extraction of surface soil is suggested to estimate surface runoff P (r2 of 0.92 for UK and 0.86 for PA soils) and subsurface drainage P (r2 of 0.82 for UK and 0.88 for PA soils), and to determine a change point in STP, which may be used in support of agricultural and environmental P management.     

Application of groundwater thresholds for trace elements on percolation water: a case study on percolation water from Northern German lowlands

The German insignificance thresholds (GFS) for groundwater, derived with an added risk approach, will soon be adopted as trigger values for percolation water entering groundwater. The physicochemical properties of the vadose zone differ considerably from those of groundwater, which may lead to difficulties in the applicability of groundwater-derived GFS to percolation water. To test the applicability of the GFS to percolation water regarding the concentration level and the field-scale variability, 46 sites in Northern Germany were sampled, including arable land, grassland, and forest, situated on three spatially dominant parent materials: sand, glacial loam, and loess. Concentrations of As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sb, Sn, V, Zn, and F were analyzed in percolation water from the transition between the unsaturated to the saturated zone. We compared median and 90th percentile values of the background concentrations with the GFS. In more than 10% of all samples, background concentrations of Cd, Co, Ni, V, or Zn exceeded the GFS. We evaluated the applicability of the GFS on field-scale medians of background concentrations taking field-scale interquartile distance and the bootstrap percentile confidence interval of the field scale median of trace element background concentrations into consideration. Statements about exceedance or nonexceedance of GFS values could only be made with acceptable statistical uncertainty (α ≤ 0.1) when operational median concentrations were about one third higher or lower than the corresponding GFS.     

Particulate phosphorus and sediment in surface runoff and drainflow from clayey soils

Recent work has shown that a significant portion of the total loss of phosphorus (P) from agricultural soils may occur via subsurface drainflow. The aim of this study was to compare the concentrations of different P forms in surface and subsurface runoff, and to assess the potential algal availability of particulate phosphorus (PP) in runoff waters. The material consisted of 91 water-sample pairs (surface runoff vs. subsurface drainage waters) from two artificially drained clayey soils (a Typic Cryaquept and an Aeric Cryaquept) and was analyzed for total suspended solids (TSS), total phosphorus (TP), dissolved molybdate-reactive phosphorus (DRP), and anion exchange resin-extractable phosphorus (AER-P). On the basis of these determinations, we calculated the concentrations of PP, desorbable particulate phosphorus (PPi), and particulate unavailable (nondesorbable) phosphorus (PUP). Some water samples and the soils were also analyzed for 137Cs activity and particle-size distribution. The major P fraction in the waters studied was PP and, on average, only 7% of it was desorbable by AER. However, a mean of 47% of potentially bioavailable P (AER-P) consisted of PPi. The suspended soil material carried by drainflow contained as much PPi (47-79 mg kg-1) as did the surface runoff sediment (45-82 mg kg-1). The runoff sediments were enriched in clay-sized particles and 137Cs by a factor of about two relative to the surface soils. Our results show that desorbable PP derived from topsoil may be as important a contributor to potentially algal-available P as DRP in both surface and subsurface runoff from clayey soils.     

Conditions affecting the release of phosphorus from surface lake sediments

Laboratory studies were conducted to determine the effect of pH and redox conditions, as well as the effect of Fe, Mn, Ca, Al, and organic matter, on the release of ortho-phosphates in lake sediments taken from Lakes Koronia and Volvi (Northern Greece). Results were evaluated in combination with experiments to determine P fractionation in the sediment. The study revealed the major effect of redox potential and pH on the release of P from lake sediments. Both lakes showed increased release rates under reductive conditions and high pH values. The fractionation experiments revealed increased mobility of the reductive P fraction as well as of the NaOH-P fraction, indicating participation of both fractions in the overall release of sediment-bound P, depending on the prevailing environmental conditions. The results were assessed in combination with the release patterns of Fe, Mn, Ca, Al, and organic matter, enabling the identification of more specific processes of P release for each lake. The basic release patterns included the redox induced reductive dissolution of P-bearing metal oxides and the competitive exchange of phosphate anions with OH- at high pH values. The formation of an oxidized surface microlayer under oxic conditions acted as a protective film, preventing further P release from the sediments of Lake Volvi, while sediments from Lake Koronia exhibited a continuous and increased tendency to release P under various physicochemical conditions, acting as a constant source of internal P loading.     

Sample intake position and loading rates from nonpoint source pollution

Paired water samples were simultaneously activated from two different vertical positions within the approach section of a flow-control structure to determine the effect of sample intake position on nonpoint runoff parameter concentrations and subsequent event loads. Suspended solids (SS), total phosphorus (TP) and organic plus exchangeable nitrogen [(Or+Ex)-N] were consistently higher throughout each runoff event when sampled from the floor of the approach section as opposed to those samples taken at midstage. Dissolved molybdate reactive phosphorus (DMRP) and ammonium (NH₄-N) concentrations did not appear to be significantly affected by the vertical difference in intake position. However, the nitrate plus nitrite nitrogen [(NO₃+NO₂)-N] concentrations were much higher when sampled from the midstage position.Although the concentration differences between the two methods were not appreciable, when evaluated in terms of event loads, discrepancies were evident for all parameters. Midstage sampling produced event loads for SS, TP, (Or + Ex)–N, DMRP, NH₄-N, and (NO₃+NO₂)-N that were 44,39,35,80,71, and 181%, respectively, of floor sampling loads. Differences in loads between the two methods are attributed to the midstage position, sampling less of the bed load. The correct position will depend on the objective; however, such differences should be recognized during the design phase of the monitoring program.This work was supported by the Soil Science Department, College of Agriculture and Life Sciences, University of Wisconsin-Madison, and by the U.S. Environmental Protection Agency, Region V., Chicago, Illinois (Grant No. G005139-01).     

Relating soil phosphorus to dissolved phosphorus in runoff: a single extraction coefficient for water quality modeling

Phosphorus transport from agricultural soils contributes to eutrophication of fresh waters. Computer modeling can help identify agricultural areas with high potential P transport. Most models use a constant extraction coefficient (i.e., the slope of the linear regression between filterable reactive phosphorus [FRP] in runoff and soil P) to predict dissolved P release from soil to runoff, yet it is unclear how variations in soil properties, management practices, or hydrology affect extraction coefficients. We investigated published data from 17 studies that determined extraction coefficients using Mehlich-3 or Bray-1 soil P (mg kg(-1)), water-extractable soil P (mg kg(-1)), or soil P sorption saturation (%) as determined by ammonium oxalate extraction. Studies represented 31 soils with a variety of management conditions. Extraction coefficients from Mehlich-3 or Bray-1 soil P were not significantly different for 26 of 31 soils, with values ranging from 1.2 to 3.0. Extraction coefficients from water-extractable soil P were not significantly different for 17 of 20 soils, with values ranging from 6.0 to 18.3. The relationship between soil P sorption saturation and runoff FRP (microg L(-1)) was the same for all 10 soils investigated, exhibiting a split-line relationship where runoff FRP rapidly increased at P sorption saturation values greater than 12.5%. Overall, a single extraction coefficient (2.0 for Mehlich-3 P data, 11.2 for water-extractable P data, and a split-line relationship for P sorption saturation data) could be used in water quality models to approximate dissolved P release from soil to runoff for the majority of soil, hydrologic, or management conditions. A test for soil P sorption saturation may provide the most universal approximation, but only for noncalcareous soils.     

Dietary strategies for reduced phosphorus excretion and improved water quality

Cost effective feeding strategies are essential to deal with P surpluses associated with intensive animal agriculture and the consequent impact on water quality. Reduction of P overfeeding, use of feed additives to enhance dietary P utilization, and development of high available phosphorus (HAP) grains have all been shown to decrease fecal P excretion without impairing animal performance. Much progress has been made, but more research will be needed to refine these strategies to maximize reductions in P excretion while maintaining animal performance. Recent research has focused on the impact of modifying dietary P on the forms of P excreted and the mobility of P in soils amended with these manures, with strong treatment trends becoming evident in the literature. In general, dietary strategies have been developed that can effectively reduce the total P concentration in manures produced, and combining strategies usually leads to greater reductions than individual practices. However, the impact of different approaches on the solubility of P in manures and amended soils has been more variable. Soluble P remains of particular concern due to links between solubility of P in manure and P losses from manure-amended soils. In this paper, we outline the major strategies for reducing dietary P in different species, review the literature on the impact of these approaches on P forms in manures and amended soils, and discuss the potential beneficial effects on animal agriculture and the environment.     

Evaluation of phosphorus transport in surface runoff from packed soil boxes

Evaluation of phosphorus (P) management strategies to protect water quality has largely relied on research using simulated rainfall to generate runoff from either field plots or shallow boxes packed with soil. Runoff from unmanured, grassed field plots (1 m wide x 2 m long, 3-8% slope) and bare soil boxes (0.2 m wide and 1 m long, 3% slope) was compared using rainfall simulation (75 mm h(-1)) standardized by 30-min runoff duration (rainfall averaged 55 mm for field plots and 41 mm for packed boxes). Packed boxes had lower infiltration (1.2 cm) and greater runoff (2.9 cm) and erosion (542 kg ha(-1)) than field plots (3.7 cm infiltration; 1.8 cm runoff; 149 kg ha(-1) erosion), yielding greater total phosphorus (TP) losses in runoff. Despite these differences, regressions of dissolved reactive phosphorus (DRP) in runoff and Mehlich-3 soil P were consistent between field plots and packed boxes reflecting similar buffering by soils and sediments. A second experiment compared manured boxes of 5- and 25-cm depths to determine if variable hydrology based on box depth influenced P transport. Runoff properties did not differ significantly between box depths before or after broadcasting dairy, poultry, or swine manure (100 kg TP ha(-1)). Water-extractable phosphorus (WEP) from manures dominated runoff P, and translocation of manure P into soil was consistent between box types. This study reveals the practical, but limited, comparability of field plot and soil box data, highlighting soil and sediment buffering in unamended soils and manure WEP in amended soils as dominant controls of DRP transport.     

Evaluating colloidal phosphorus delivery to surface waters from diffuse agricultural sources

Colloid-facilitated phosphorus (P) delivery from agricultural soils in different hydrological pathways was investigated using a series of laboratory and field experiments. A soil colloidal P test was developed that yields information on the propensity of different soils to release P attached to soil colloids. The relationship between turbidity of soil extracts and total phosphorus (TP) was significant (r2 = 0.996, p < 0.001) across a range of agricultural soils, and a strong positive relationship (r2 = 0.86, p < 0.001) was found between "colloidal P" (H2O-CaCl2 extracts) and turbidity. Linear regression of the proportion of fine clay (<2 microm) for each soil type evaluated against the (H2O-CaCl2) colloidal P fraction gave a weak but positive relationship (r2 = 0.38, p = 0.082). The relative contribution of different particle-size fractions in transporting P in agricultural runoff from grassland soils was evaluated using a randomized plot experiment. A significant difference (p = 0.05) in both TP and reactive phosphorus (RP) in subsurface flow was recorded for different particle-size fractions, with most TP transferred either in association with the 2-microm fraction or with the 0.001-microm or smaller fractions. Total P concentrations in runoff were higher from plots receiving P amendments compared with the zero-P plots; however, these differences were only significant for the >0.45-microm particle-size fractions (p = 0.05), and may be evidence of surface applications of organic and inorganic fertilizers being transferred through the soil either as intact organic colloids or attached to mineral particles. Our results highlight the potential for drainage water to mobilize colloids and associated P during rainfall events.