RISK AND MONITORING SYSTEM FOR SOIL CONCERNING NITRATE DIRECTIVE IN ROMANIA

Catalin SIMOTA National Research and Development Institute for Soil Science, Agricultural Chemistry and Environment Bucharest ROMANIA

ICPA performed a previous delineation of NVZs in Romania which was mainly based on the soil map. The characteristics of the soil according to the variables runoff and leaching capacity, provide the nitrate vulnerability of the region. As such this method provided for every soil type vulnerability scores for different criteria (e.g. wet front hydraulic conductivity; maximum available water; the general soil type; presence of an impermeable layer, etc.). By combining all these criteria for each soil type, general vulnerability scores were assigned.

Whereas the method of ICPA mainly considers the leaching capacity of the soil, the vulnerability of groundwater is also affected by the stability of nitrate in the groundwater. Similar to the previous method of RISSA, this stability can also be assessed as a function of different criteria such as hydraulic conductivity of groundwater layers, the hydraulic gradient and the presence or absence of reducing compounds. All these criteria can be combined in a general vulnerability score for groundwater, considering both the leaching capacity of the soil and the stability of nitrate in the groundwater reservoir.

Delineation of Recharge Areas

The first step of the delineation of the NVZs was the delineation of the recharge areas, where surface water is allowed to enter into an aquifer. These areas are particularly vulnerable to various pollutants present in the surface water. Outside of the recharge areas the vulnerability of groundwater was not considered because the impact of nitrate pollution can be neglected.

The delineation of recharge areas was mainly based on the phreatic groundwater map

As phreatic aquifers chiefly occur in plains with clastic sediments, a delineation of these plains was prepared. This delineation was compared to the information from a digital terrain model, in which areas with slopes steeper than 8% are considered as mountain areas In the code of good agricultural practice, distinction is made between plains, hills and mountains. For the sake of simplicity, only two classes are retained in the delineation of NVZ. Hills and mountains are considered as one class. Generally, in these mountain areas the impact of runoff will be more important than the leaching effects towards groundwater bodies.

A comparison of these two maps reveals that both delineations are quite similar. Nearly all the phreatic aquifers are situated in the plains shown by the extracted DTM map. However, the few phreatic aquifers in the areas with slopes steeper than 8%, are in karst regions or in fissured rock types. The infiltration rate can be high in these areas, and as such, the groundwater table is vulnerable for nitrate pollution. These regions are included in the recharge areas derived from the data layer with phreatic aquifers. As a result, MAP 1 will be used as final delineation of the recharge areas.

Delineation of Nitrate Vulnerable Zones for Surface Waters

Nitrates mainly reach surface waters by groundwater discharge. This effect has been accounted for in the assessment of groundwater vulnerability. To avoid double-counting, nitrate contamination of surface waters by groundwater discharge will not be considered here. Next to groundwater discharge, nitrates may also reach the river system by superficial runoff or by flooding of nitrate contaminated soils. In mountain areas, superficial runoff can be considerable but the extent of flooding areas is usually rather small. On plains, the volume of surface runoff is very limited but large flooding areas may appear.

Delineation of Nitrate Vulnerable Zones for Surface Waters

On the one hand, the amount of runoff in mountain areas will be affected by the soil type. The higher the infiltration capacity of a soil, the smaller the precipitation part that contributes the surface water runoff.

As such, the soil criteria affecting this infiltration (like the drainage classes, the hydraulic conductivity, the maximum available water, the parental material and the texture) have an influence on the nitrate vulnerability of the surface water. High vulnerability scores can be given for criteria that cause higher runoff rates.

Delineation of Nitrate Vulnerable Zones for Surface Waters

On the other hand, a vulnerability factor could be introduced for assessing nitrate vulnerability of surface waters in mountain areas, based on the distance of a place to the most nearby river. In mountain areas, the risk that superficial runoff will actually reach a river network, is proportional to the distance to the nearest river.

The further the distance, the higher the chance that water will infiltrate or evaporate and will never reach the river. Vulnerable zones are consequently the zones nearby rivers.

Delineation of Nitrate Vulnerable Zones for Surface Waters

On the plains, characterized by slopes of less than 8%, the effect of runoff can be neglected, as mentioned earlier.
The vulnerable zones can be restricted to the possible flooding areas, as nitrates in the soil can reach the surface waters in a direct way only during floods (i.e. not passing through major groundwater reserves).

Delineation of Nitrate Vulnerable Zones for Groundwater

The delineation of nitrate vulnerable zones in the groundwater bodies was only performed in recharge areas. For the assessment of nitrate vulnerability, the subdivided aquifers (subzones) were connected in Hydrogeological Homogenous Zones (HHZs), with comparable physical and chemical conditions and where natural nitrate removal inside the aquifer systems follows similar processes.

Delineation of Nitrate Vulnerable Zones for Groundwater

The following type of subzones were united into one HHZ: Adjacent subzones that are subdivided on the above mentioned aquifer map, as they fall within different river basins; Adjacent subzones of similar geological age, similar type of aquifer and properties (e.g. conductivity, infiltration, rock material); Adjacent subzones in the same floodplain, terraces or alluvium from the same river system; Subzones that are not adjacent one to each other, but within a short distance and with the same geological age, similar kind of aquifer and similar properties (e.g. conductivity, infiltration, rock material).

In order to assess the vulnerability of a HHZ, the risk that nitrates can occur in the groundwater was determined. In fact, the presence of nitrates in the groundwater depends on three factors: the supply of nitrates from the surface to the groundwater table; the distribution of nitrates by transport with the groundwater; redox reactions, including a decrease of nitrate concentrations due to reduction of the nitrates.

The first of these factors, mainly depend on external sources of contamination that cannot be connected to the HHZ. These external sources can be diffuse nitrate pollution due to agriculture (application of manure on the field), as well as point pollution sources e.g. resulting from failing sewer systems.

On the other hand, the supply of nitrates to the phreatic groundwater bodies is also affected by the leaching potential of the soil.

The other two factors (i.e. horizontal transport of nitrates and redox reactions) are solely related to the HHZ. First of all, the distribution of nitrates, both horizontally and vertically, will contribute to the vulnerability of an HHZ. An HHZ will be more sensitive if nitrate can percolate faster into the subsurface. HHZs with high infiltration rates will thus be assessed as more vulnerable.

The distribution of nitrates, and as such the vulnerability, also depends on redox conditions in the groundwater. Nitrate is only stable when dissolved oxygen is present in the groundwater. Under oxic conditions, oxygen is used in oxidation processes (e.g. the oxidation of pyrite and/or organic matter), but after the removal of oxygen, in anoxic conditions, nitrate will act as the oxydans during these oxidation processes, resulting in the reduction of the nitrate

Redox zones

The nitrate vulnerability of the HHZs was based on following criteria:

the hydraulic conductivity; the hydraulic gradient; the thickness of the unsaturated zone; the oxidation status of the rocks during deposition or formation; the thickness of the water saturated zone of the aquifer;

For the conductivity of the groundwater water, scores were based on the K values, obtained from literature:
1 low vulnerability: K < 20 m/day 2 moderate vulnerability : K = 20 100 m/day 3 high vulnerability: K > 100 m/day 4 extremely vulnerable: Karst and fissured rocks. Discharge values (Q) are used instead of K values;

The scores for the oxidation status during rock formation could be divided in two groups: oxidation was possible or difficult. As nitrate is more stable when oxygen is available, the rocks that were possibly affected to oxidation during formation, will be more vulnerable: 1 low vulnerability: 2 vulnerable: Alluvial deposits; Other type of rock formations;

For the reduction capacity of the soil, scores were assessed by the presence or absence of organic material or pyrite:
1 low vulnerability: presence of organic material or pyrite; 2 vulnerable: absence of organic material or pyrite;

The gradient of the groundwater table causes horizontal migration of pollutants. Because there was no accurate information about groundwater flow, the gradient was calculated as the gradient of the ground surface (Digital Terrain Model). On plains the groundwater table runs more or less parallel with the ground surface (->): 1 low vulnerability: 2 vulnerable: 3 high vulnerability gradient values <2; gradient between 2 and 4; gradient >4;

The thickness of the unsaturated zone is derived from the soil map, with soils in flooding areas of river systems being saturated the most: 1 low vulnerability:recent soils 2 vulnerable: hydromorph soils 3 very vulnerable: supplementary class water All other soil types were considered as not vulnerable (= 0).

The sum of the scores of all criteria resulted in a general score for the nitrate vulnerability of each HHZ

HHZ Geological Age ROGW01 ROGW02 ROGW03 ROGW04 ROGW05 ROGW06 ROGW07 ROGW08 ROGW09 ROGW10 ROGW11 ROGW12 ROGW13 ROGW14 ROGW15 ROGW16 ROGW17 Cuaternar Paleogen-Cuarternar Triasic-Cretacic Cuaternar (depozite Holocene-Pleistocene) Cuaternar Precambrian Cuaternar Cuaternar Cuarternar Paleozoic-triasicJurasic Precambrian superior Paleozoic Jurasic-Cretacic Carbonifer inferior Cretacic superior Precambrian superiorPaleozoic Jurasic-Cretacic Catchment Somes -Tisa Somes -Tisa Somes -Tisa; Crisuri Somes -Tisa Somes -Tisa Somes -Tisa; Siret Mures; Crisuri Mures Mures Mures Mures; Banat Mures Mures Mures Mures Mures Mures

Oxidation during Formation 1 2 2 1 1 2 1 1 1 2 2 2 2 2 2 2 2

Conductivity

Reduction Capacity 2 1 2 1 1 2 2 2 2 2 2 2 2 2 2 2 2

Thickness of Unsatured Zone 0 0 0 0 1 0 1 0 1 0 0 0 0 0 0 0 0

Gradient

Final Vulnerability Score 7 10 11 7 8 11 7 6 8 11 11 11 11 11 11 11 11

3 4 4 3 3 4 2 2 2 4 4 4 4 4 4 4 4

1 3 3 2 2 3 1 1 2 3 3 3 3 3 3 3 3

Assessment per NVZ

For the assessment of the vulnerability of groundwater bodies and surface waters, the data layer with nitrate concentrations was attached to the corresponding nitrate vulnerable zone (NVZg and NVZs respectively). As such, for each NVZg/NVZs the average and variation in the pollution data per NVZ can be presented. For each NVZ these statistics are provided separately for all measuring points inside and outside of the communas. The mean value of the actual nitrate pollution within one zone is calculated with the data outside of the communas. The data from inside of the communas will be used to locate any point pollution.

Assessment per NVZ

In a next phase a score is provided based on the mean actual pollution. The standard for nitrate in potable water of 50 mg/l (EU Drinking Water Directive, 1998 and WHO, 2004) is considered as the upper threshold. For the delineation of areas that are not affected by nitrate pollution, the mean background values of nitrate in EU groundwater of 10 mg/l is used (UNEP, 2004)

Assessment per NVZ

0 no pollution (and natural contamination), values lower then 10mg/l; 1 little pollution, values between 10 and 25mg/l; 2 moderately polluted, values between 25 and 50 mg/l; 3 heavily polluted, values higher then 50mg/l.

Pollution matrix showing different classes of risk and monitoring actions, based on potential vulnerability and actual pollution
0 A A B E actual pollution 1 2 A C C B B D E G 3 F F G G

no low intermediate high

A) B) C) D) E) F) G)

low risk --> least concern monitoring results show low contamination, the potential risk is low to moderate --> monitorring program to look for possible pollution unexpected intermediate pollution values in areas with no or small potential risk --> look for reason, monitoring campaign need to be adapted (point source, bad delineation) moderate values in an area weighted as intermediate --> moderate monitoring, attention for pollution sources low measurement values, but the area is weighted as high risk. A --> precautions for pollution, no aggriculture, and many monitoring wells! High values measured, while no problem has been expected. --> look for reason, monitoring campaign need to be adapted (point source, bad delineation) important risk, higher pollution vallues --> cleaning up, many monitorring wells

potential vulnerability

Assessment per comuna

Subsequently, the selected communas are projected on the NVZs which are combined with the data from wells. Each communa is situated at least in one NVZ with a given potential vulnerability. If monitoring points are available inside the NVZ, the actual pollution status of the communa can be estimated based on these monitoring data. For some NVZs, no monitoring wells were available. For example, in karst areas, nitrate concentrations in groundwater have not been monitored. In this case, an appropriate monitoring program will be proposed that aims to assess whether or not increased nitrate concentrations appear inside the NVZ. The density of monitoring wells is set proportional to the potential nitrate vulnerability. Each communa is thus evaluated together with the local NVZ. When a communa is located on the border of two NVZs, the communa is split in two parts and evaluated twice.

HHZ A B C

pot low high low

act 0 3 2

villages 1 + 2 3

HHZ A B B C

new code 1a 1b 2b 3c

HHZ A B B C

pot low high high low

act 0 3 3 2

Methodology for Groundwater Monitoring Wells

The location of the wells that are installed to detect and monitor diffuse pollution should be according to the following conditions: inside arable land; at a distance of minimum 100 m downstream of houses, farms and industry; at a distance of minimum five times the width of running surface water; at a distance of minimum 100 m downstream of nature reserves and forests; at a distance of minimum 100 m downstream of manure and waste disposals; easily accessible to drilling companies and laboratories; at a distance of minimum 100 m of watersheds and border zones between different HHZs.

Score A If the combination of the scores for a selected communa is evaluated as A, then both the potential vulnerability and the actual pollution is assessed as low. As a result the selected communa is of least concern. The existing monitoring network will be sufficient in this case. There is no need for additional monitoring.

Score B If the combination of the scores for a selected communa is evaluated as B, then the monitoring results show low nitrate contamination, while the potential risk is assessed as low to moderate. Therefore, this communa should be monitored in order to prevent possible pollution in the future. The existing monitoring network may be sufficient, with a sampling frequency of once per several years.

Score C or F If the combination of the scores for a selected communa is evaluated as C or F, the actual pollution is not in line with the assessed potential vulnerability. Although the potential vulnerability is assessed as low, the actual pollution shows respectively intermediate and high values. In this case, it can be important to look for point pollution (i.e. high values within communas or the presence of outliers in the data set). In this case, appropriate measures should be taken in function of the type of point pollution (e.g. wastewater treatment plant). To follow up point pollution problems more detailed monitoring campaigns need to be foreseen, with wells and surface water observation points upstream an downstream of the point source. A sampling frequency of once per several years is advised. This, way the long-term efficiency of pollution abatement strategies can be evaluated. If no indication for point pollution was found, an evaluation as C or F may indicate an error of the delineation of the vulnerable zones.

Score D If the combination of the scores for a selected communa is evaluated as D, then an intermediate potential vulnerability and a moderate actual nitrate pollution are calculated. Measures should be taken to reduce the production of nitrates in the area and the evolution of the water quality should be closely monitored. Yearly or 2-yearly sampling is advised, with monitoring wells located upstream and downstream of the village. Depending on the density of the existing monitoring network, a frequent (e.g. 2-yearly) sampling of the existing wells may be sufficient or additional wells will need to be installed.

Score E or G If the combination of the scores for a selected communa is evaluated as E or G, then the potential vulnerability is assessed as high. No matter if the actual pollution is small (E) or high (G) the monitoring campaign should be rather intensive. A yearly sampling frequency is advised. Existing wells can be used, but depending on the density of the existing monitoring network, it will most probably be necessary to install additional wells, so that several measuring locations upstream and downstream of the village are present. Agricultural activities should be decreased, and precautions for possible pollution need to be made. In case of an evaluation as G, measures should be taken in order to clean up the actual pollution.

Soil monitoring
For each groundwater/surface water monitoring site measurements of nitrate concentration in soil (0-30, 30-60, 60-90 cm depth) in recharging areas are to be done 2 times per year (spring/winter) Sampling design needs to be adapted to specific hydrogeological conditions, land use and local agriculture practices